Bpa-free coatings

ABSTRACT

Provided are poly(AAG)-compositions, and corresponding coatings, foams, and coated articles. Also provided are methods for preparing the poly(AAG)-compositions and corresponding reagents including, e.g., polyol-AAG compositions. Coatings using the poly(AAG)-compositions may be useful for, e.g., replacing bisphenol-A cross-linked coatings used in food and beverage containers, coating metal articles, and the like.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority from U.S. Provisional PatentApplication No. 62/146,237, fled on Apr. 10, 2015, which is incorporatedby reference herein in its entirety.

BACKGROUND

Bispheol-A (BPA) is a cross-linker for synthetic resins used ascoatings, and began to replace resins based on natural oils (oleoresins)in the mid-1970s. BPA-based coatings have high corrosion resistancecompared to oleoresins and are widely used, e.g., in food packaging. Inthe United States, over 300 billion beer, beverage, and food cans arecoated with half a million metric tons of BPA-containing epoxy resinseach year, and the global market is more than twice that large. Althoughthere are currently no U.S. Food and Drug Administration (FDA) or otherU.S. regulatory restrictions on the use of BPA-based resins in most foodcontainers, BPA-related health hazards have been recognized byregulators, policymakers, and consumers. Controversy over healthimplications has caused concern over the use of BPA in food packaging.BPA is banned from use in applications such as infant feeding plasticbottles, and California recently listed BPA as a hazardous material.

There is much interest in cost-effective and functional replacements forBPA-based epoxy resins in can coatings that may contact food. Desirablecharacteristics for alternative coatings are numerous and challenging,including coating integrity (adhesion, strength, flexibility,pH/corrosion resistance, and the like) under sterilization, handling,and storage, no effect on food taste, compliance with FDA guidelines ondirect food contact use, cost-effective, compatible with establishedmanufacturing processes, and the like.

Many attempts to develop a viable solution have been made. Natural oilsmay be functionalized with hydroxyl or carboxyl groups and may beconverted to polyesters and polyurethanes for use in coatings, inks,adhesives, foams, and the like. However, oleoresins often exhibit poorcorrosion resistance. For example, it is believed that acidic tomatojuice readily damages oleoresin coatings. Chemistries such asvinylation, acrylation, polyesterifcation, polyolefinination, and use ofa variety of cross-linkers have been explored, but have not beensuccessful because of failure in one or more desirable characteristics,such as flexibility, adhesion, application method, cure speed, corrosionresistance, or hydrolysis under low pH.

Some epoxy-based resin alternatives have been investigated usingalternative cross-linkers, such as diglycidyl ethers of n-alkyldiphenolates, isosorbide, and bisguaracol. However, these alternativesare costly and have been reported to suffer from problems such asestrogen receptor activity, epichlorohydrin toxicity, and poorhydrolytic stability.

The present application appreciates that developing corrosion resistantresins. e.g., for replacing BPA-cross-linked resins in can coatings, maybe a challenging endeavor.

SUMMARY

In one embodiment, In various embodiments, a method for preparing a AAGcomposition is provided. The method may include providing apoly-functional compound including two or more functional groups. Eachfunctional group nay independently be hydroxy, amino, or alkenyl. Themethod may include reacting the poly-functional compound underconditions effective to form the AAG composition by one or more of thefollowing. For example, the method may include reacting thepoly-functional compound under conditions effective to form the AAGcomposition by contacting the poly-functional compound with a ketenecompound, wherein the poly-functional compound includes at least onehydroxy group. The method may include reacting the poly-functionalcompound under conditions effective to form the AAG composition bycontacting the poly-functional compound with a β-ketoester, wherein thepoly-functional compound includes at least one hydroxy or amino group.The method may include reacting the poly-functional compound underconditions effective to form the AAG composition by contacting thepoly-functional compound with a peroxo reagent and one or more of: aβ-ketoimide, a β-ketoester, and a β-ketoacid, wherein thepoly-functional compound includes at least one alkenyl group. The methodmay include reacting the poly-functional compound under conditionseffective to form the AAG composition by contacting the poly-functionalcompound with a mercaptoalkanol in the presence of an initiatoreffective to form a mercaptoalkanol-substituted compound. Thepoly-functional compound may include at least one alkenyl group. Themethod may include further reacting the mercaptoalkanol-substitutedcompound with one or more of: the β-ketoester and the β-ketoacideffective to form the AAG composition.

In another embodiment, a method for preparing an AAG composition isprovided. The method may include contacting a poly-functional compoundwith a β-ketoester to form a reaction mixture. The poly-functionalcompound may include one or more of: a hydroxyl group; and an aminogroup. The method may include allowing the poly-functional compound andthe β-ketoester to react substantially in the absence of solventeffective to form the AAG composition.

In one embodiment, a method for preparing a polyol-AAG composition isprovided. The method may include contacting an unsaturated polyol with aperoxo reagent and a β-ketoimide to form a reaction mixture. The methodmay include allowing the unsaturated polyol, the peroxo reagent, and theβ-ketoimide to react effective to form the polyol-AAG composition.

In one embodiment, a method for preparing a poly(AAG)-composition isprovided. The method may include contacting an AAG composition with across-linking compound to form a reaction mixture. The method mayinclude allowing the AAG composition and the cross-linking compound toreact effective to form the poly(AAG) composition. The AAG compositionmay exclude a triglyceride-AAG composition.

In another embodiment, a method for preparing a poly(AAG)-β-ketoestercomposition is provided. The method may include contacting a AAGcomposition with a cross-linking compound to form a reaction mixture.The method may include allowing the AAG composition and thecross-linking compound to react effective to form thepoly(AAG)-β-ketoester composition.

In one embodiment, a poly(AAG)-composition is provided. Thepoly(AAG)-composition may include a polyfunctional moiety derived from apolyol unit, a polyamine unit, a polyalkene unit, or a combination orcomposite thereof. The poly(AAG)-composition may include a β-ketoestergroup bonded to an alkyl chain of the polyfunctional moiety. Thepoly(AAG)-composition may include one or more of the following. Thepoly(AAG)-composition may include an amide group bonded to a carbon ofthe alkyl chain that is alpha to a ketone of the β-ketoester such thatthe poly(AAG)-composition includes a poly(AAG)amido-β-ketoestercomposition. The poly(AAG)-composition may include an amine group bondedto a carbon on the alkyl chain that is beta to a ketone of theβ-ketoester such that the poly(AAG)-composition comprises apoly(AAG)amino-β-ketoester composition. The poly(AAG)-composition mayinclude a hydrazone group bonded to a keto-carbon of the β-ketoestergroup such that the poly(AAG)-composition comprises apoly(AAG)hydrazone-β-ketoester composition.

In another embodiment, a poly(AAG)-β-ketoester composition is provided.The poly(AAG)-β-ketoester composition may include: a polyol unit; aβ-ketoester group bonded to an alkyl chain of the polyol unit. Thepoly(AAG)-β-ketoester composition may include an amide group bonded to acarbon of the alkyl chain that may be alpha to a ketone of theβ-ketoester such that the poly(AAG)-β-ketoester composition includes apolyol polyamido-β-ketoester composition. The poly(AAG)-β-ketoestercomposition may include an amine group bonded to a carbon on the alkylchain that may be beta to a ketone of the β-ketoester such that thepoly(AAG)-β-ketoester composition includes a polyolpolyamino-β-ketoester composition. The poly(AAG)-β-ketoester compositionmay include a hydrazone group bonded to a keto-carbon of the β-ketoestergroup such that the poly(AAG)-β-ketoester composition includes a polyolpolyhydrazone-β-ketoester composition.

In one embodiment, an article is provided. The article may include asurface coated with a poly(AAG)-composition.

In another embodiment, an article is provided. The article nay include asurface coated with a poly(AAG)-β-ketoester composition.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying figures, which are incorporated in and constitute apart of the specification, illustrate example methods and compositionsand are used merely to illustrate example embodiments.

FIG. 1 is an FTIR spectrum of an example soy-AAG (“soy-PK”), as preparedin EXAMPLES 2A and 2B.

FIG. 2 is a table showing the physical properties of an example soy-AAG(“soy-PK”).

FIG. 3 is a graph illustrating the relative cure rates, via TGA, of anexample soy-AAG (“soy-PK”) and a commercial bio-based polyol withCYMEL™-303 cross-linker.

FIG. 4 is a table showing the performance properties of an examplesoy-AAG (“soy-PK”) CYMEL™-303-cured resin as compared to commercial BPAresin.

FIG. 5 is a graph illustrating the relative corrosion performances, viaEIS, of an example soy-AAG (“soy-PK”) CYMEL™-303-cured resin, commercialBPA resin, commercial BPA resin alternative, and aluminum.

FIG. 6 is a graph illustrating the toxicity performance, via BGILUCassay, of an example soy-AAG (“soy-PK”) CYMEL™-303-cured resin withrespect to anti-estrogenic activity.

FIG. 7 is a graph illustrating the toxicity performance, via BGILUCassay, of an example soy-AAG (“soy-PK”) CYMEL™-303-cured resin withrespect to estrogenic activity.

DETAILED DESCRIPTION

In various embodiments, a method for preparing a triglyceride-AAGcomposition is provided. The method may include contacting an epoxidizedtriglyceride composition with an epoxy-reactive nucleophilic compound.The epoxy-reactive nucleophilic compound may be AAG (acetoacetylgroup)-substituted. The epoxy-reactive nucleophilic compound may beAAG-unsubstituted. The method may include allowing the epoxidizedtriglyceride composition to react with the AAG-substitutedepoxy-reactive nucleophilic compound effective to form thetriglyceride-AAG composition. The method may include allowing theepoxidized triglyceride composition to react with the AAG-unsubstitutedepoxy-reactive nucleophilic compound effective to form an intermediateproduct. The method may include reacting the intermediate product with aβ-ketoacid or a β-ketoester effective to form the triglyceride-AAGcomposition.

In some embodiments, the method may include allowing the epoxidizedtriglyceride composition to react with the AAG-unsubstitutedepoxy-reactive nucleophilic compound effective to form the intermediateproduct, e.g., ending with isolation of the intermediate product.

In many embodiments, the method may include contacting the epoxidizedtriglyceride composition with the AAG-substituted epoxy-reactivenucleophile in the form of the β-ketoacid to form a reaction mixture.The method may include allowing the epoxidized triglyceride compositionand the β-ketoacid to react effective to form the triglyceride-AAGcomposition.

As used herein, the term “AAG” means an acetoacetyl group. For example,triglyceride-methyl-AAG and polyol-methyl-AAG may refer to,respectively:

As used herein, a “β-ketoacid” means a group including a carboxylic acidseparated from a carbonyl by one intervening carbon atom, e.g.,—C(═O)CH₂CO₂H. Likewise, as used herein, a “β-ketoester” means a groupincluding a carboxylic acid ester separated from a carbonyl by oneintervening carbon atom, e.g., —C(═O)CH₂CO₂R.

As used herein, an epoxidized triglyceride means a triester of glycerol,CH(CH₂OH)₂, with at least one epoxide group in or on at least one fattyacid side-chain.

As used herein, an epoxy-reactive nucleophilic compound means a compoundcapable of reacting with an epoxide, e.g., a compound containing atleast one nucleophilic functional group capable of a nucleophilic attackon an electrophilic epoxy carbon of the epoxidized triglyceride. Thenucleophilic attack may lead to, for example, ring-opening of theepoxide, covalent bond formation between the nucleophilic functionalgroup of the epoxy-reactive nucleophilic compound and the electrophilicepoxy carbon of the epoxidized triglyceride, and the like Examplenucleophilic functional groups include, for example, hydroxy, amino,thiol, carboxy, and the like. For example, an epoxy-reactivenucleophilic compound may include a nucleophilic functional group, e.g.,hydroxy, amino, thiol, carboxy, phosphine, and the like. Further, forexample, an epoxy-reactive nucleophilic compound may include anucleophilic functional group which may produce a nucleophiliccarbanion, e.g., a carbonyl-containing compound, such as an enolate.

In many embodiments, an epoxidized triglyceride composition may includethe epoxidized triglyceride. The epoxidized triglyceride composition maybe characterized by a percentage by weight of the epoxidizedtriglyceride of at least about one or more of: 50, 60, 70, 8, 90, 95,96, 97, 98, 99, 99.5, and 99.9. The epoxidized triglyceride compositionmay consist essentially of, or consist of, the epoxidized triglyceride.The epoxidized triglyceride composition may include a portion of freeglycerol. The epoxidized triglyceride composition may include one ormore glycerol monoesters, diesters, and triesters. Each ester group inthe one or more glycerol monoesters, diesters, and triesters maycorrespond to one of a saturated fatty acid, an unsaturated fatty acid,and an epoxidized fatty acid. The epoxidized triglyceride compositionmay consist essentially of, or consist of, the glycerol monoesters,diesters, and triesters; the glycerol diesters and triesters; or theglycerol triesters. For example, the epoxidized triglyceride compositionmay consist essentially of the epoxidized triglyceride, with smallamounts of glycerol or glycerol monoesters, diesters, and triestersincluding saturated fatty acid groups and unsaturated fatty acid groups.

As used herein, a saturated fatty acid means a carboxylic acid with aC₁-C₂₆ alkyl group, e.g., decanoic acid (C₉ chain), dodecanoic acid (C₁₁chain), and the like. As used herein, an unsaturated fatty acid means acarboxylic acid with a C₁-C₂₆ alkenyl group including at least onecarbon-carbon double bond, e.g., 2-decenoic acid, 2-dodecenoic acid, andthe like. As used herein, an epoxidized fatty acid is a carboxylic acidwith a C₁-C₂₆ alkyl group including at least one epoxide group. Theepoxidized fatty acid may correspond to the unsaturated fatty acidwherein the at least carbon-carbon double bond may be epoxidized. Thesaturated fatty acid groups, unsaturated fatty acid groups, andepoxidized fatty acid groups may be optionally substituted. e.g., withone or more hydroxyl substituents.

In various embodiments of the method, the epoxidized triglyceridecomposition may include a compound represented by Formula I:

Each R^(1-I) may independently be H,

provided that at least one R^(1-I) may be:

R² may be optionally hydroxylated C₂-C₂₆ alkyl. R² may be optionallyhydroxylated C₂-C₂₅ alkyl or optionally hydroxylated C₂-C₂₅ alkenyl. R⁴may be a bond, optionally hydroxylated C₁-C₂₅ alkyl, optionallyhydroxylated C₂-C₂₅ alkenyl or optionally hydroxylated C₂-C₂₅epoxyalkyl.

In several embodiments, the epoxidized triglyceride composition mayinclude a hydroxyl value in mg KOH/g of one or more of about: 5, 10, 15,20, 25, 50, 75, 100, 250, 500, 750, 1000, 1250, 1500, 1750, and 1800; ora range between any two of the preceding values, for example, betweenabout 5 and about 1800. The epoxidized triglyceride composition mayinclude a number of epoxide functional groups per triglyceride of one ormore of about: 1, 2, 3, 4, 5, 6, 7, or 8, or a range between any two ofthe preceding values, for example, between about 2 and about 8.

In various embodiments, the epoxidized triglyceride composition may bederived by epoxidaion of an unsaturated fatty acid triglyceride esterobtained from any organism, including, for example, plants, mammals,reptiles, insects, fish, mollusks, crustaceans, fungi, algae, diatoms,and the like. In some embodiments, the epoxidized triglyceridecomposition may exclude those derived from insects or marine,non-terrestrial plant and animal sources, e.g., marine plants (e.g.,water hyacinth), marine mammals, marine reptiles, fish, mollusks,crustaceans, marine microorganisms (e.g., fungi, bacteria, algae,diatoms), and the like, or in some embodiments, the epoxidizedtriglyceride composition may exclude those derived from insects ormarine sources such as marine plants (e.g., water hyacinth), marinemammals, marine reptiles, fish, mollusks, crustaceans, marinemicroorganisms (e.g., fungi, bacteria, algae, diatoms), and the like.The epoxidized triglyceride composition may include epoxidized chains offatty acid esters derived from one or more of: linolenic acid, linoleicacid, oleic acid, myristoleic acid, palmitoleic acid, sapienic acid,elaidic acid, vaccenic acid, linoelaidic acid, α-linolenic acid,arachidonic acid, eicosapentanenoic acid, erucic acid, docsahexaenoicacid, ricinoleic acid, and the like. The epoxidized triglyceridecomposition may include epoxidized chains of fatty acid esters derivedfrom one or more of: coconut oil, palm kernel oil, palm oil, cottonseedoil, wheat germ oil, soybean oil, olive oil, corn oil, sunflower oil,safflower oil, hemp oil, canola/rapeseed oil, castor oil, and the like.The epoxidized triglyceride composition may include epoxidized chains offatty acid esters derived from oil of one or more of: legume seeds,non-legume seeds, and animal fat. In some embodiments, animal fatincludes terrestrial animals and excludes marine animals. The epoxidizedtriglyceride composition may include epoxidized chains of fatty acidesters derived from soybean oil.

In several embodiments, the epoxidized triglyceride composition mayinclude a compound represented by Formula II:

R′ may be C₁-C₄ alkyl. R² may be optionally hydroxylated C₂-C₂₅ alkyl oroptionally hydroxylated C₂-C₂₅ alkenyl. R⁴ may be a bond, or optionallyhydroxylated C₁-C₂₅ alkyl, C₂-C₂₅ alkenyl, or C₂-C₂₅ epoxyalkyl.

In some embodiments, the epoxidized triglyceride composition may be oneof at least partially: hydrogenated, hydroxylated, and hydrolyzed. Theepoxidized triglyceride composition may be characterized by a percentageby weight of epoxidized triglyceride of at least about one or more of:50, 60, 70, 80, 90, 95, 96, 97, 98, 99, 99.5, and 99.9. The β-ketoacidmay be represented by Formula III:

R⁵ may be optionally hydroxylated C₁-C₈ alkyl, optionally hydroxylatedC₂-C₈ alkenyl, optionally hydroxylated C₆-C₁₀ aryl, or optionallyhydroxylated C₄-C₁₀ heteroaryl. R⁸ may be H, optionally hydroxylatedC₁-C₈ alkyl, or optionally hydroxylated C₆-C₁₀ aryl.

In many embodiments, the β-ketoacid may include one or more of:3-oxobutanoic acid, 3-oxopentanoic acid, 3-oxohexanoic acid,3-oxo-3-phenylpropanoic acid, and the like.

In several embodiments, the method may include contacting the epoxidizedtriglyceride composition and the epoxy-reactive nucleophilic compound,e.g., the β-ketoacid, in the presence of an acid catalyst. The acidcatalyst may include one or more of: p-toluene sulfonic acid; methanesulfonic acid, a C₁-C₈ carboxylic acid; a C₁-C₈ halocarboxylic acid,e.g., trifluoromethane sulfonic acid, chloroacetic acid, dichloroaceticacid, trichloroacetic acid, and the like; a polymeric sulfonic acidresin; boron trifluoride; 9-BBN, and the like. In some embodiments, themethod may include contacting the epoxidized triglyceride compositionand the epoxy-reactive nucleophilic compound, e.g., the β-ketoacid, inthe presence of a base. The base may include one or more of: pyridine,trimethylamine, triethylamine, and the like.

In some embodiments, the method may include heating, e.g., of theepoxidized triglyceride composition and the epoxy-reactive nucleophiliccompound, to a temperature in ° C. of at least about one or more of: 30,40, 50, 60, 70, 80, 90, and 100. The method may include allowingreaction effective to form the triglyceride-AAG composition, e.g., ofthe epoxidized triglyceride composition and the epoxy-reactivenucleophilic compound or of the intermediate product and the β-ketoacidor β-ketoester, for a period of time in minutes of at least about one ormore of: 5, 10, 15, 20, 30, 40, 6, 90, 120, 150, 170, and 200.

In several embodiments, the triglyceride-AAG composition may include atriglyceride-AAG. The triglyceride-AAG may include a fatty acid ester;at least one hydroxyl group bonded to an alkyl chain of the fatty acidester; and a β-ketoester group bonded to a carbon atom alpha to a carbonatom bearing the hydroxyl group. For example, the triglyceride-AAGcomposition may include a compound represented by Formula IV:

Each R^(1-IV) may independently be H,

provided that at least one R^(1-IV) is not H, or alternatively, providedthat at least one R^(1-IV) may be:

R² may be optionally hydroxylated C₂-C₂₅ alkyl or optionallyhydroxylated C₂-C₂₅ alkenyl. R³ may be H or:

R⁴ may be a bond, optionally hydroxylated C₁-C₂₅ alkyl, optionallyhydroxylated C₂-C₂₅ alkenyl, or optionally hydroxylated C₂-C₂₅epoxyalkyl. R⁵ may be optionally hydroxylated C₁-C₈ alkyl, optionallyhydroxylated C₂-C₈ alkenyl, optionally hydroxylated C₆-C₁₀ aryl, oroptionally hydroxylated C₄-C₁₀ heteroaryl.

In many embodiments, the epoxy-reactive nucleophilic compound may besubstituted with an AAG group, i.e., an AAG-substituted epoxy-reactivenucleophile. For example, the AAG-substituted epoxy-reactive nucleophilemay include an AAG-substituted hydroxy acid in some embodiments, theAAG-substituted epoxy-reactive nucleophilic compound may include one ormore of: dimethylol propionic acid, lactic acid, citric acid, tartaricacid, diphenolic acid, and the like. At least one hydroxyl group of oneor more of: dimethylol propionic acid, lactic acid, citric acid,tartaric acid, diphenolic acid, and the like, may be substituted with anAAG group. For example, an AAG-substituted epoxy-reactive nucleophileincluding, for example, lactic acid, may be represented by:

In many embodiments, the triglyceride-AAG composition may include acompound represented by:

Each R^(1-IV) may independently be H,

provided that at least one R^(1-IV) may be:

R² may be optionally hydroxylated C₂-C₂₅ alkyl or C₂-C₂₅ alkenyl. R³ maybe H, or:

R⁴ may be a bond, or optionally hydroxylated C₁-C₂₅ alkyl, C₂-C₂₅alkenyl, or C₂-C₂₅ epoxyalkyl. R_(a) may be C₁-C₆ alkyl, branched alkyl,carboxy-substituted alkyl, aryl, or aralkyl. R⁵ may be optionallyhydroxylated C₁-C₈alkyl, C₂-C₈ alkenyl, C₆-C₁₀ aryl, or C₄-C₁₀heteroaryl.

In many embodiments, the AAG-unsubstituted epoxy-reactive nucleophilecompound may be represented by:

X—R_(b)—Y

X may be —OH, —SH, —NH₂, or —NHR_(f). R_(f) may be optionallyhydroxylated C₁-C₆alkyl, Y may be —OH, —SH, —NH₂, or —NHR_(f). R_(b) maybe optionally substituted C₁-C₆ alkyl, or aryl.

In some embodiments, the epoxy-reactive nucleophilic compound mayinclude one or more of: an alkanolamine, e.g., a mono C₁-C₈alkanolamine, a di C₁-C₈ alkanolamine, and the like: a mercaptoalkanol,e.g., a C₁-C₈ mercaptoalkanol; a diol, e.g., a C₁-C₈ diol; ahydroxyphenol, an aminophenol, a mercaptophenol, and the like. Forexample, the epoxy-reactive nucleophilic compound may include one ormore of: ethanolamine, diethanolamine, mercaptoethanol, ethylene glycol,propylene glycol, ethylenediamine, ethane-1,2-dithiol, pyrogallol,catechol, resorcinol, hydroquinone, lignin, and the like.

The intermediate product may be represented by:

R² may be optionally hydroxylated C₂-C₂₅ alkyl or C₂-C₂₅ alkenyl. R⁴ maybe a bond, or optionally hydroxylated C₁-C₂₅ alkyl, C₂-C₂₅ alkenyl, orC₂-C₂₅ epoxyalkyl. R_(b) may be optionally carboxylated C1-C6 alkyl,branched alkyl, or aryl. X is O, S, NH, or N-alkyl. Y is OH, SH, NH₂, orNH-alkyl. R^(1-X) may be H,

R²′ may be optionally hydroxylated C₂-C₂₆ alkyl.

In some embodiments, the method may include reacting the intermediateproduct with a β-ketoester to form the triglyceride-AAG composition. Theβ-ketoester may be represented by:

R_(e) may be C₁-C₄ alkyl. R⁵ may be optionally hydroxylated C₁-C₈ alkyl,C₂-C₈ alkenyl, C₆-C₁₀ aryl, or C₄-C₁₀ heteroaryl. R⁸ may be H, oroptionally hydroxylated C₁-C₈ alkyl or C₆-C₁₀ aryl.

In many embodiments, the method may include allowing the epoxidizedtriglyceride composition to react with the AAG-unsubstitutedepoxy-reactive nucleophilic compound effective to form the intermediateproduct. The method may include reacting the intermediate product withthe β-ketoacid or the β-ketoester effective to form the triglyceride-AAGcomposition.

In several embodiments, the triglyceride-AAG composition may include acompound represented by:

Each R^(1-IV) may independently be H,

provided that at least one R^(1-IV) may be:

R² may be optionally hydroxylated C₂-C₂₅ alkyl or C₂-C₂₅ alkenyl. R³ maybe H, or:

R⁴ may be a bond, or optionally hydroxylated C₁-C₂₅ alkyl, C₂-C₂₅alkenyl, or C₂-C₂₅ epoxyalkyl. R_(b) may be C₁-C₆ alkyl, branched alkyl,or aryl, R⁵ may be optionally hydroxylated C₁-C₈ alkyl, C₂-C₈ alkenyl,C₆-C₁₀ aryl, or C₄-C₁₀ heteroaryl. X may be O, S, NH, or NR_(f). Y maybe O, S, NH, or NR_(f). R_(f) ma be optionally hydroxylated C₁-C₆ alkyl.

In some embodiments, the triglyceride-AAG composition may include ahydroxyl value in mg KOH/g of one or more of about: 5, 10, 15, 20, 25,50, 75, 100, 250, 50, 750, 1000, 1250, 1500, 1750, and 1800; or a rangebetween any two of the preceding values, for example, between about 5and about 1800. For example, the triglyceride-AAG composition mayinclude a hydroxyl value greater than the epoxidized triglyceridecomposition.

In various embodiments, a method fro preparing a triglyceride-AAGcomposition is provided. The method may include contacting anunsaturated triglyceride with a peroxo reagent and one or more of: aβ-ketoimide, a β-ketoester, and a β-ketoacid to form a reaction mixture.The method may include allowing the unsaturated triglyceride, the peroxoreagent, and one or more of: the β-ketoimide, the β-ketoester, and theβ-ketoacid to react effective to form the triglyceride-AAG composition.

In several embodiments, the method may include contacting theunsaturated triglyceride with a peroxo reagent and the β-ketoimide toform the reaction mixture. The method may include allowing theunsaturated triglyceride, the peroxo reagent, and the β-ketoimide toreact effective to form the triglyceride-AAG composition.

In some embodiments, the method may include pre-mixing the peroxoreagent and one or more of the β-ketoimide and the β-ketoacid prior tocontacting the unsaturated triglyceride. The method may includepre-mixing the peroxo reagent and one or more of the β-ketoimide and theβ-ketoacid at a reduced temperature, e.g., less than about 25° C. Themethod may include pre-mixing the unsaturated triglyceride and one ormore of the β-ketoimide and the β-ketoacid prior to contacting theperoxo reagent.

The method may include allowing the unsaturated triglyceride, the peroxoreagent, and one or more of: the β-ketoimide, the β-ketoester, and theβ-ketoacid to react at a temperature in ° C. of at least about one ormore of: 0, 10, 20, 30.40, 50, 60, 70, 80, 90, and 100. The method mayinclude allowing the unsaturated triglyceride, the peroxo reagent, andone or more of the β-ketoimide, the β-ketoester, and the β-ketoacid toreact for a period of time in minutes of at least about one or more of:5, 10, 15, 20, 30, 40, 60, 90, 120, 150, 170, and 200.

In several embodiments, the method may include, after forming thetriglyceride-AAG composition, contacting the reaction mixture with areducing agent effective to consume at least a portion of remainingperoxo reagent. Suitable reducing reagents may include, for example,sodium sulfite, sodium thiosulfate, and the like. The method mayinclude, after forming the triglyceride-AAG composition, purifying thetriglyceride-AAG composition by one or more of contacting the reactionmixture with one of: water, aqueous brine, and aqueous mild acid:separating an aqueous layer from the reaction mixture, contacting thereaction mixture to a chromatography solid phase: eluting thetriglyceride-AAG composition from the chromatography solid phase toprovide the triglyceride-AAG composition in at least partly purifiedform.

In various embodiments, the unsaturated triglyceride may be representedby Formula V:

Each R^(1-V) may independently be H, or:

provided that at least one R^(1-V) may be:

R²′ may be optionally-hydroxylated C₂-C₂₆ alkyl. R² may be optionallyhydroxylated C₂-C₂₅ alkyl or optionally hydroxylated C₂-C₂₅ alkenyl. R⁴may be a bond, optionally hydroxylated C₁-C₂₅ alkyl, or optionallyhydroxylated C₂-C₂₅ alkenyl.

In various embodiments, the unsaturated triglyceride may be obtainedfrom any organism, including, for example, plants, mammals, reptiles,insects, fish, mollusks, crustaceans, fungi, algae, diatoms, and thelike. In some embodiments, the unsaturated triglyceride may excludethose derived from insects or marine, non-terrestrial plant and animalsources, e.g., marine plants (e.g., water hyacinth), marine mammals,marine reptiles, fish, mollusks, crustaceans, marine microorganisms(e.g., fungi, bacteria, algae, diatoms), and the like, or in someembodiments, the unsaturated triglyceride may exclude those derived frominsects or marine sources such as marine plants (e.g., water hyacinth),marine mammals, marine reptiles, fish, mollusks, crustaceans, marinemicroorganisms (e.g., fungi, bacteria, algae, diatoms), and the like.The unsaturated triglyceride may include an unsaturated fatty acid groupderived from one or more of: linolenic acid, linoleic acid, oleic acid,myristoleic acid, palmitoleic acid, sapienic acid, elaidic acid,vaccenic acid, linoelaidic acid. α-linolenic acid, arachidonic acid,eicosapentanenoic acid, erucic acid, docosahexaenic acid, ricinoleicacid, and the like. The unsaturated triglyceride may include anunsaturated fatty acid group derived from one or more of, coconut oil,palm kernel oil, palm oil, cottonseed oil, wheat germ oil, soybean oil,olive oil, corn oil, sunflower oil, safflower oil, hemp oil,canola/rapeseed oil, castor oil, and the like. The unsaturatedtriglyceride may include an unsaturated fatty acid group derived fromoil of one or more of legume seeds, non-legume seeds, animal fat, andthe like. In some embodiments, animal fat includes terrestrial mammalsand excludes marine mammals. The unsaturated triglyceride may include anunsaturated fatty acid group derived from soybean oil.

In several embodiments, the β-ketoimide may be represented by FormulaVI:

R⁵ may be optionally hydroxylated C₁-C₈ alkyl, optionally hydroxylatedC₂-C₈ alkenyl, optionally hydroxylated C₆-C₁₀ aryl, or optionallyhydroxylated C₄-C₁₀ heteroaryl. R⁹ may be C₁-C₈ alkyl or C₆ aryloptionally substituted with one or more of: nitro, carbonyl, haloalkyl,and halogen.

As used herein, halogen means fluoro, chloro, bromo, and iodo.Haloalkyls may include, for example, trifluoromethyl, and the like.

In various embodiments, the S-ketoimide may be represented by FormulaVII:

R⁵ may be optionally hydroxylated C₁-C₈ alkyl, optionally hydroxylatedC₂-C₈ alkenyl, optionally hydroxylated C₆-C₁₀ aryl, or optionallyhydroxylated C₄-C₁₀ heteroaryl. R¹⁰ may be C₂-C₆ alkyl, C₃-C₅heteroaryl, or C₆ aryl optionally substituted with one or more of:nitro, carbonyl, haloalkyl, and halogen. For example, the β-ketoimidemay be represented by Formula VIII:

The β-ketoimide may also be represented by Formula IX:

R⁵ may be optionally hydroxylated C₁-C₈ alkyl, optionally hydroxylatedC₂-C₈ alkenyl, optionally hydroxylated C₆-C₁₀ aryl, or optionallyhydroxylated C₄-C₁₀ heteroaryl.

In some embodiments, the peroxo reagent may be hydrogen peroxide. Forexample, the peroxo reagent may include one or more of: hydrogenperoxide, manganese dioxide, sodium percarbonate, potassiumpercarbonate, sodium perborate, potassium perborate, and the like.

In various embodiments, the β-ketoester or β-ketoacid may be representedby:

R_(e) may be H or C₁-C₄ alkyl; R⁵ may be optionally hydroxylated C₁-C₈alkyl, C₂-C₈ alkenyl, C₆-C₁₀ aryl, or C₄-C₁₀ heteroaryl, and R⁸ may beH, or optionally hydroxylated C₁-C₈ alkyl or C₆-C₁₀ aryl.

In many embodiments, the triglyceride-AAG composition may include atriglyceride-AAG. The triglyceride-AAG may include: a fatty acid estersubstituted with at least one hydroxyl group on an alkyl chain of thefatty acid ester; and a β-ketoester group bonded to a carbon atom alphato a carbon atom bearing the hydroxyl group. For example, thetriglyceride-AAG composition may include a compound represented byFormula X:

Each R^(1-X) may independently be H,

provided that at least one R^(1-X) may be:

R²′ may be optionally hydroxylated C₂-C₂₆ alkyl. R² may be optionallyhydroxylated C₂-C₂₅ alkyl or optionally hydroxylated C₂-C₂₅ alkenyl. R³may be H, or:

R⁴ may be a bond, optionally hydroxylated C₁-C₂₅ alkyl, optionallyhydroxylated C₂-C₂₅ alkenyl, or optionally hydroxylated C₂-C₂₅epoxyalkyl. R⁵ may be optionally hydroxylated C₁-C₈ alkyl, optionallyhydroxylated C₂-C₈ alkenyl, optionally hydroxylated C₆-C₁₀ aryl, oroptionally hydroxylated C₄-C₁₀ heteroaryl.

The triglyceride-AAG composition may include a hydroxyl value in mgKOH/g of one or more of about: 5, 10, 15, 20, 25, 50, 75, 1, 250, 500,750, 1000, 1250, 1500, 1750, and 1800; or a range between any two of thepreceding values, for example, between about 5 and about 1800. Forexample, the triglyceride-AAG composition may include a hydroxyl valuegreater than the unsaturated triglyceride.

In various embodiments, a method for preparing a triglyceride-AAGcomposition is provided. The method may include contacting anunsaturated triglyceride with a mercaptoalkanol in the presence of aninitiator to form a first reaction mixture. The method may includeallowing the unsaturated triglyceride and the mercaptoalkanol to reacteffective to provide a mercaptoalkanol-substituted triglyceride. Themethod may include contacting the mercaptoalkanol-substitutedtriglyceride with one or more of: β-ketoester and a β-ketoacid to form asecond reaction mixture. The method may include allowing themercaptoalkanol-substituted triglyceride and one or more of theβ-ketoester and the β-ketoacid to react effective to provide thetriglyceride-AAG composition.

In many embodiments, the initiator may include one or more of: heat,ultraviolet light, and a catalyst. For example, the initiator mayinclude a ultraviolet light and a catalyst. For example, the initiatormay include heat and a catalyst. For example, the catalyst may include.Ru(bpy)₃Cl₂.

In many embodiments, the unsaturated triglyceride may be represented

Each R^(1-V) independently may be H,

provided that at least one R^(1-V) may be:

R²′ may be optionally hydroxylated C₂-C₂₆ alkyl. R² may be optionallyhydroxylated C₂-C₂₅ alkyl or C₂-C₂₅ alkenyl. R⁴ may be a bond, oroptionally hydroxylated C₁-C₂₅ alkyl, or C₂-C₂₅ alkenyl.

In some embodiments, the mercaptoalkanol may be, e.g., a C₁-C₈mercaptoalkanol, for example, the mercaptoalkanol may include one ormore of: thioglycerol and mercaptoethanol, and the like.

In many embodiments, the mercaptoalkanol-substituted triglyceride may berepresented by:

R² may be optionally hydroxylated C₂-C₂₅ alkyl or C₂-C₂₅ alkenyl. R⁴ maybe a bond, or optionally hydroxylated C₁-C₂₅ alkyl, or C₂-C₂₅ alkenyl.R_(b) may be optionally carboxylated C1-C6 alkyl, branched alkyl, oraryl. R^(1-X) may be H,

R²′ may be optionally hydroxylated C₂-C₂₆ alkyl.

In many embodiments, the β-ketoacid or β-ketoester may be representedby:

R_(e) may be H or C₁-C₄ alkyl. R⁵ may be optionally hydroxylated C₁-C₈alkyl, C₂-C₈ alkenyl, C₆-C₁₀ aryl, or C₄-C₁₀ heteroaryl. R⁸ may be H, oroptionally hydroxylated C₁-C₈ alkyl or C₆-C₁₀ aryl.

In several embodiments, the triglyceride-AAG composition may include acompound represented by:

Each R^(1-X) independently may be H,

provided that at least one R^(1-X) may be:

R²′ may be optionally hydroxylated C₂-C₂₆ alkyl. R² may be optionallyhydroxylated C₂-C₂₅ alkyl or C₂-C₂₅ alkenyl. R⁴ may be a bond, oroptionally hydroxylated C₁-C₂₅ alkyl, or C₂-C₂₅ alkenyl. R_(b) may beC₁-C₆ alkyl, branched alkyl, or aromatic hydrocarbon. R⁵ may beoptionally hydroxylated C₁-C₈ alkyl, C₂-C₈ alkenyl, C₆-C₁₀ aryl, orC₄-C₁₀ heteroaryl.

In various embodiments, a method for preparing a triglyceride-AAGcomposition is provided. The method may include contacting ahydroxylated triglyceride with a ketene compound to form a reactionmixture. The method may include allowing the hydroxylated triglycerideand ketene compound to react effective to provide the triglyceride-AAGcomposition.

In several embodiments, the hydroxylated triglyceride may be representedby:

Each R^(1-V) independently may be H,

provided that at least one R^(1-V) may be:

R²′ may be optionally hydroxylated C₂-C₂₆ alkyl. R² may be optionallyhydroxylated C₂-C₂₅ alkyl or C₂-C₂₅ alkenyl. R⁴ may be a bond, oroptionally hydroxylated C₁-C₂₅ alkyl, or C₂-C₂₅ alkenyl.

In many embodiments, the ketene compound may include one or more of:4-methyleneoxetan-2-one, 4-ethylidene-3-methyloxetan-2-one, and4-benzylidene-3-phenyloxetane-2-one. In some embodiments, the ketenecompound may be derived from one or more of: a diazo ketone and anα-halo acyl halide. The ketene compound may be optionally substitutedwith one or more of: C₁-C₈ alkyl and C₆-C₁₀ aryl.

In several embodiments, the triglyceride-AAG composition may include acompound being represented by.

Each R^(1-X) may independently be H,

provided that at least one R^(1-X) may be:

R²′ may be optionally hydroxylated C₂-C₂₆ alkyl. R² may be optionallyhydroxylated C₂-C₂₅ alkyl or C₂-C₂₅ alkenyl. R⁴ may be a bond, oroptionally hydroxylated C₁-C₂₅ alkyl, C₂-C₂₅ alkenyl. R⁵ may beoptionally hydroxylated C₁-C₈ alkyl, C₂-C₈ alkenyl, C₆-C₁₀ aryl, orC₄-C₁₀ heteroaryl.

In various embodiments, a triglyceride-AAG composition is provided. Thetriglyceride-AAG composition may include a fatty acid ester. Thetriglyceride-AAG composition may include a β-ketoester group bonded toan alkyl chain of the fatty acid ester.

In several embodiments, the triglyceride-AAG composition may include thefatty acid ester. The triglyceride-AAG composition may include at leastone hydroxyl group bonded to an alkyl chain of the fatty acid ester. Thetriglyceride-AAG composition may include β-ketoester group bonded to acarbon atom of the alkyl chain that may be alpha to a carbon atombearing the hydroxyl group.

In many embodiments, the triglyceride-AAG composition may include acompound represented by:

Each R^(1-X) may independently be H,

provided that at least one R^(1-X) may be:

R²′ may be optionally hydroxylated C₂-C₂₆ alkyl. R² may be optionallyhydroxylated C₂-C₂₅ alkyl or C₂-C₂₅ alkenyl. R⁴ may be a bond, oroptionally hydroxylated C₁-C₂₅ alkyl, C₂-C₂₅ alkenyl. R⁵ may beoptionally hydroxylated C₁-C₈ alkyl, C₂-C₈ alkenyl, C₆-C₁₀ aryl, orC₄-C₁₀ heteroaryl.

In many embodiments, the triglyceride-AAG composition may include acompound represented by Formula X:

Each R^(1-X) may independently be H,

provided that at least one R^(1-X) may be:

R²′ may be optionally hydroxylated C₂-C₂₆ alkyl. R² may be optionallyhydroxylated C₂-C₂₅ alkyl or optionally hydroxylated C₂-C₂₅ alkenyl. R³may be H, or:

R²′ may be a bond, optionally hydroxylated C₁-C₂₅ alkyl, optionallyhydroxylated C₂-C₂₅ alkenyl, or optionally hydroxylated C₂-C₂₅epoxyalkyl. R⁵ may be optionally hydroxylated C₁-C₈ alkyl, optionallyhydroxylated C₂-C₈ alkenyl, optionally hydroxylated C₆-C₁₀ aryl, oroptionally hydroxylated C₄-C₁₀ heteroaryl.

In various embodiments, a triglyceride-AAG composition is provided. Thetriglyceride-AAG composition may include a fatty acid ester. Thetriglyceride-AAG may include a linking group, the linking group beingrepresented by:

X ma be —OH, —SH, —NH₂, or NHR_(f). R_(b) may be optionally substitutedC₁-C₆ alkyl or aryl. R_(f) may be optionally hydroxylated C₁-C₆ alkyl.The triglyceride-AAG may include a β-ketoester group. The linking groupmay be bonded to an alkyl chain of the fatty acid ester via X and theβ-ketoester group may be bonded via an ester moiety to R.

In several embodiments, the triglyceride-AAG composition may include acompound represented by:

Each R^(1-X) may independently be H,

provided that at least one R^(1-X) may be:

R²′ may be optionally hydroxylated C₂-C₂₆ alkyl. R² may be optionallyhydroxylated C₂-C₂₅ alkyl or C₂-C₂₅ alkenyl. R⁴ may be a bond, oroptionally hydroxylated C₁-C₂₅ alkyl, or C₂-C₂₅ alkenyl. R_(b) may beC₁-C₆ alkyl, branched alkyl, or aromatic hydrocarbon. R⁵ may beoptionally hydroxylated C₁-C₈ alkyl, C₂-C₈ alkenyl, C₆-C₁₀ aryl, orC₄-C₁₀ heteroaryl.

In several embodiments, the triglyceride-AAG may further include atleast one hydroxyl group. The at least one hydroxyl group may be bondedto the alkyl chain of the fatty acid ester. The linking group may bebonded to a carbon atom of the alkyl chain that is alpha to a carbonatom bearing the at least one hydroxyl group.

In many embodiments, the triglyceride-AAG composition may include acompound represented by:

Each R^(1-X) may independently be H,

provided that at least one R^(1-X) may be:

R²′ may be optionally hydroxylated C₂-C₂₅ alkyl. R² may be optionallyhydroxylated C₂-C₂₅ alkyl or C₂-C₂₅ alkenyl. R³ may be H, or:

R⁴ may be a bond, or optionally hydroxylated C₁-C₂₅ alkyl, C₂-C₂₅alkenyl, or C₂-C₂₅ epoxyalkyl. R_(b) may be optionally carboxylatedC₁-C₆ alkyl, branched alkyl, or aromatic hydrocarbon. R⁵ may beoptionally hydroxylated C₁-C₈ alkyl, C₂-C₈ alkenyl, C₆-C₁₀ aryl, orC₄-C₁₀ heteroaryl. X may be O, S, or N.

In various embodiments, a method for preparing apolytriglyceride-β-ketoester composition is provided. The method mayinclude contacting a triglyceride-AAG composition with a cross-linkingcompound to form a reaction mixture. The method may include allowing thetriglyceride-AAG composition and the cross-linking compound to reacteffective to form the polytriglyceride-β-ketoester composition.

In many embodiments, the triglyceride-AAG composition may include acompound represented by Formula X:

Each R^(1-X) independently may be H,

provided that at least one R^(1-X) may be:

R²′ may be optionally hydroxylated C₂-C₂₆ alkyl. R² may be optionallyhydroxylated C₂-C₂₅ alkyl or optionally hydroxylated C₂-C₂₅ alkenyl. R³may be H, or:

R⁴ may be a bond, optionally hydroxylated C₁-C₂₅ alkyl, optionallyhydroxylated C₂-C₂₅ alkenyl, or optionally hydroxylated C₂-C₂₅epoxyalkyl. R⁵ may be optionally hydroxylated C₁-C₈ alkyl, optionallyhydroxylated C₂-C₈ alkenyl, optionally hydroxylated C₆-C₁₀ aryl, oroptionally hydroxylated C₄-C₁₀ heteroaryl.

In some embodiments, the triglyceride-AAG composition may include afatty acid group derived from oil of one or more of legume seeds,non-legume seeds, and animal fat. The triglyceride-AAG composition mayinclude a fatty acid group derived from soybean oil. The method mayinclude contacting the triglyceride-AAG composition and thecross-linking compound in the presence of a surfactant. The surfactantmay include one or more of: tegostab B4690, Silstab 2000,polysiloxane-polyoxyalkylene block copolymer, and the like.

In several embodiments, the method may include contacting thetriglyceride-AAG composition and the cross-linking compound neat, e.g.,substantially in the absence of organic solvent. The method may includecontacting the triglyceride-AAG composition and the cross-linkingcompound in the presence of an organic solvent, e.g., acetone, methylethyl ketone, and the like. The method may include contacting thetriglyceride-AAG composition and the cross-linking compound in thepresence of one or more of: water; a blowing agent; and a base. The basemay include one or more of: magnesium hydroxide, zirconium hydroxide,aluminum hydroxide, and the like.

In some embodiments, the method may include contacting thetriglyceride-AAG composition and the cross-linking compound in diepresence of a polyol-AAG. The method may include heating the reactionmixture to a temperature in ° C. of at least one or more of: 140, 150,160, 170, 180 and 200. The method may include allowing thetriglyceride-AAG composition and the cross-linking compound to react fora period of time in minutes of at least about one or more of: 5, 10, 15,20, 30, 40, 60, 90, 120, 150, 170, and 200.

In some embodiments, the method may include: applying the reactionmixture onto a surface; and heating the reaction mixture and the surfaceeffective to form the polytriglyceride-β-ketoester composition as across-linked coating on the surface. The method may include contactingthe triglyceride-AAG composition and the cross-linking compound at about25° C. for less than 3 minutes prior to spraying the reaction mixtureonto the surface. The method may include heating the reaction mixtureand the surface at a temperature of about 180° C. for 20 minuteseffective to form the polytriglyceride-β-ketoester composition as thecross-linked coating on the surface. The surface may be a metal surface.The surface may be an interior surface of a food or beverage container,e.g., a can. The surface may include a foil or metal packaging material.The surface may include one or more of: low carbon steel, aluminum,anodized aluminum, silver, and alloys or mixtures thereof. The surfacemay be one or more of an interior surface or an exterior surface of amedical device. The polytriglyceride-β-ketoester composition may form across-linked coating on one or more of the interior surface and theexterior surface of the medical device. Further, silver may be includedby one or more of; the interior surface, the exterior surface, and thepolytriglyceride-β-ketoester composition forming the cross-linkedcoating. The silver may be in ionic or oxide form.

In several embodiments, the method may include contacting thetriglyceride-AAG composition and the cross-linking compound at about 25°C.; and pouring the reaction mixture into a mold, the mold coated in amold release agent. The cross-linking compound may include one or moreof: a diisocyanate, a triisocyanate, and a tetraisocyanate. Thecross-linking compound may include a polymer that includes more than oneisocyanate. The cross-linking compound may include one or more of:Luprinate M20, PMDI, Desmodur DA-L Desmodur DN, Bayhydur 302, VESTANAT®T, VESTANAT® HB, VESTANAT® HT, VESTANAT® B, VESTANAT® DS (EvonikResource Efficiency GmbH. Essen, Germany), and like isocyanatecross-linking reagents.

In some embodiments, the polytriglyceride-β-ketoester composition mayinclude a polytriglyceride polyamido-β-ketoester including a fatty acidester, a β-ketoester bonded to an alkyl chain of the fatty acid ester;and an amide group bonded to a carbon alpha to a ketone of theβ-ketoester. For example, the polytriglyceride polyamido-β-ketoester maybe represented by Formula XI:

Each R^(1-XI) independently may be H,

provided that at least one R^(1-XI) may be:

R²′ may be optionally hydroxylated C₂-C₂₆ alkyl. R² may be optionallyhydroxylated C₂-C₂₅ alkyl or optionally hydroxylated C₂-C₂₅ alkenyl. R³may be H or AAG:

R⁴ may be a bond, optionally hydroxylated C₁-C₂₅ alkyl, optionallyhydroxylated C₂-C₂₅ alkenyl, or optionally hydroxylated C₂-C₂₅epoxyalkyl. R⁵ may be optionally hydroxylated C₁-C₈ alkyl, optionallyhydroxylated C₂-C₈ alkenyl, optionally hydroxylated C₆-C₁₀ aryl, oroptionally hydroxylated C₄-C₁₀ heteroaryl. R⁶ may be C₂-C₆ alkyl, C₆-C₁₀aryl, C₁-C₆ alkyl-C₆-C₁₀ aryl, C₃-C₅ heteroaryl, or C₁-C₆ alkyl-C₃-C₅heteroaryl. R_(b) may be optionally carboxylated C₁-C₆ alkyl, branchedalkyl, or aryl. X may be O, S, or N. R⁷ may be:

In some embodiments, the polytriglyceride-β-ketoester composition mayinclude a hydroxyl value in mg KOH/g of one or more of about: 5, 10, 15,20, 25, 5075, 100, 250, 500, 750, 1000, 1250, 1500, 1750, and 1800; or arange between any two of the preceding values, for example, betweenabout 5 and about 1800.

As used herein, a “hemiaminal” may refer to a compound including a—NR(CR₂′)OH group or —CR′(NR)(OH) group. As used herein, a “hemiaminalether” may refer to a compound including a —NR(CR₂′)OR″ group or—CR′(NR(OR″) group. As used herein, a “hemithioaminal” may refer to acompound including a —NR(CR₂′)SH group or —CR′(NR)(SH) group. As usedherein, a “hemiaminal thioether” may refer to a compound include a—NR(CR₂′)SR″ group or —CR′(NR)(SR″). R, and R′ may be H, alkyl, or aryl.R″ may be alkyl or aryl. As used herein used herein, a “hemiaminal”.“hemiaminal ether”, “hemithioaminal”, and “hemiaminal thioether” may berepresented by, respectively:

In many embodiments, the cross-linking compound may include one or moreof: a hemiaminal, a hemiaminal ether, a hemiaminal thioether an aromatichemiaminal, an aromatic hemiaminal ether, an aromatic hemiaminalthioether, a polymer including a hemiaminal, a polymer including ahemiaminal ether, a polymer including a hemiaminal thioether, and thelike. For example, the cross-linking compound may include hemiaminalcross-linking compounds (e.g., the CYMEL™ series from Allnex USA, Inc.,Alpharetta, Ga.) such as one or more of: CYMEL™ 303. CYMEL™ 300, CYMEL™301, CYMEL™ 303 LF, CYMEL™ 304, CYMEL™ 350, CYMEL™ 3745, CYMEL™ XW 3106,CYMEL™ MM-100, CYMEL™ 323, CYMEL™ 325, CYMEL™ 327, CYMEL™ 328, CYMEL™385, CYMEL™ 370, CYMEL™ 373, CYMEL™ 380, and the like.

In several embodiments, the method may include contacting thetriglyceride-AAG composition and the cross-linking compound in thepresence of an acid catalyst. The acid catalyst may include one or moreof: p-toluene sulfonic acid; methane sulfonic acid; a C₁-C₈ carboxylicacid; a C₁-C₈ halocarboxylic acid, e.g., trifluoromethane sulfonic acid,chloroacetic acid, dichloroacetic acid, trichloroacetic acid, and thelike; a polymeric sulfonic acid resin; boron trifluoride; and the like.The acid may include a Lewis acid. As used herein, a Lewis acid means anelectron-deficient species that may accept electrons from a Lewis base.Suitable Lewis acids may be based on main group metals such as aluminum,boron, silicon, and tin, as well as early (titanium, zirconium) and late(iron, copper, zinc) d-block metals. A suitable Lewis acid may betrimethoxy boron, trimethoxyaluminum, 9-BBN, and the like. For example,methoxide or hydroxide from the hemiaminal or hemiaminal ether would bethe Lewis base and result in an eta complex with the Lewis acid.

In several embodiments, the polytriglyceride-β-ketoester may include atriglyceride polyamino-β-ketoester. The triglyceridepolyamino-β-ketoester may include a fatty acid ester. The triglyceridepolyamino-4-ketoester may include a β-ketoester group bonded to an alkylchain of the fatty acid ester. The triglyceride polyamino-β-ketoestermay include an amine group bonded to the alkyl chain at a carbon beta toa ketone of the β-ketoester. For example, the triglyceridepolyamino-β-ketoester may be represented by Formula XII:

Each R^(1-XII) may independently be H,

provided that at least one R^(1-XII) may be:

R²′ may be optionally hydroxylated C₂-C₂₆ alkyl. R² may be optionallyhydroxylated C₂-C₂₅ alkyl or optionally hydroxylated C₂-C₂₅ alkenyl. R³may be H, or:

R⁴ may be a bond, optionally hydroxylated C₁-C₂₅ alkyl, optionallyhydroxylated C₂-C₂₅ alkenyl, or optionally hydroxylated C₂-C₂₅epoxyalkyl. R⁵ may be optionally hydroxylated C₁-C₈ alkyl, optionallyhydroxylated C₂-C₈ alkenyl, optionally hydroxylated C₆-C₁₀ aryl, oroptionally hydroxylated C₄-C₁₀ heteroaryl. R⁶′ may be optionallyhydroxylated C₂-C₆ alkyl, optionally hydroxylated C₄-C₁₀ aryl,optionally hydroxylated C₁-C₆ alkyl-C₆-C₁₀ aryl, optionally hydroxylatedC₃-C₅ heteroaryl, or optionally hydroxylated C₁-C₆ alkyl-C₃-C₅heteroaryl. R_(b) may be optionally carboxylated C₁-C₆ alkyl, branchedalkyl, or aryl. X may be O, S, or N. R⁶′ may be: CH₂OH, CH—OCH₃, CH₂SH,CH₂SCH₃,

R⁷′ may be:

In various embodiments, the cross-linking compound may include adihydrazine or a dihydrazide. For example, the cross-linking compoundmay include one or more of: adipic dihydrazide, sebacic dihydrazide,oxalyl dihydrazide, succinic dihydrazide, maleic dihydrazide, malicdihydrazide, isophthalic dihydrazide, terephthalic dihydrazide, and thelike.

In some embodiments, the polytriglyceride-β-ketoester may include atriglyceride polyhydrazone-β-ketoester. The triglyceridepolyhydrazone-β-ketoester may include a fatty acid ester. The glyceridepolyhydrazone-β-ketoester may include a β-ketoester group bonded to analkyl chain of the fatty acid ester. The triglyceridepolyhydrazone-β-ketoester may include a hydrazone group bonded to theketo-carbon of the β-ketoester. For example, the product may berepresented by Formula XIII:

Each R^(1-XIII) may independently be H,

provided that at least one R^(1-XIII) may be:

R²′ may be optionally hydroxylated C₂-C₂₆ alkyl. R² may be optionallyhydroxylated C₂-C₂₅ alkyl or optionally hydroxylated C₂-C₂₅ alkenyl. R³may be H, or:

R⁴ may be a bond, optionally hydroxylated C₁-C₂₅ alkyl, optionallyhydroxylated C₂-C₂₅ alkenyl, or optionally hydroxylated C₂-C₂₅epoxyalkyl. R⁵ may be optionally hydroxylated C₁-C₈ alkyl, optionallyhydroxylated C₂-C₈ alkenyl, optionally hydroxylated C₆-C₁₀ aryl, oroptionally hydroxylated C₄-C₁₀ heteroaryl. R⁶′″ may be C₂-C₆ alkyl,C₄-C₁₀ carboxylalkyl, C₄-C₁₀ sulfonylalkyl, C₆-C₁₀ aryl, C₁-C₆alkyl-C₆-C₁₀ aryl, C₃-C₅ heteroaryl, or C₁-C₆ alkyl-C₃-C₅ heteroaryl.R_(b) may be optionally carboxylated C₁-C₆ alkyl, branched alkyl, oraryl. X may be O, S, or N. R⁷″ may be:

In some embodiments, the cross-linking compound may include at least onediazonium group. The cross-linking compound may include at least twodiazonium groups.

In some embodiments, the cross-linking compound may include an aldehyde,for example, formaldehyde.

In some embodiments, the cross-linking compound may include at least twoα,β-unsaturated carbonyl groups. For example, the cross-linking compoundmay be represented by Formula XIV:

R may be CH₂CH₂, CH₂(CH₃)CH, (CH₂CH₂OCH₂CH₂)_(n), orCH₂(CH₃)CHOCH₂(CH₃)CH)_(n); and n may be an integer from 1 to 50.

In many embodiments, the crosslinking compound may include a polyamine.For example, the polyamine may include a diamine, triamine, and thelike. The polyamine may be aliphatic or cycloaliphatic. The polyaminemay be aromatic, aryl, or aralkyl. The polyamine may include a mixtureof aliphatic, cycloaliphatic, and aromatic polyamines. For example, thepolyamine may include any of the ANACAMINE® series (Air Products,Allentown, Pa.), e.g., ANACAMINE® 2049, ANACAMINE® 1110. ANACAMINE®1482. ANACAMINE® 1608, ANACAMINE® 1617LV, ANACAMINE® 1638. ANACAMINE®1693, ANACAMINE® 1769, ANACAMINE® 1784, ANACAMINE® 1856. ANACAMINE®1884, ANACAMINE® 1922A, ANACAMINE® 2014FG, ANACAMINE® 2021, ANACAMINE®2072, ANACAMINE® 2074, ANACAMINE® 2089M, ANACAMINE® 2143, ANACAMINE®2280, and the like. The polyamine crosslinking agent may crosslinktriglyceride-AAG compositions via imine or enamine linkages.

In several embodiments, the polytriglyceride-β-ketoester may include atriglyceride polyenamine-β-ketoester. The triglyceridepolyenamine-β-ketoester may include a fatty acid ester. The triglyceridepolyenamine-β-ketoester may include a β-ketoester group bonded to analkyl chain of the fatty acid ester. The triglyceridepolyenamine-β-ketoester may include an enamine group bonded to aketo-carbon of the β-ketoester.

As used herein, a “keto-carbon” or “keto-carbonyl” may refer to acarbonyl carbon, i.e., C(═O). As used herein, a “imine” may refer to anamine condensed onto a carbonyl, i.e., C(═NR). As used herein, an“enamine” may refer to a amine condensed onto a carbonyl, followed bytautomerization, i.e., C═C—NR.

In several embodiments, the triglyceride polyenamine-β-ketoester may berepresented by:

Each R^(1-XIII) may independently be H,

provided that at least one R^(1-XIII) may be:

R²′ may be optionally hydroxylated C₂-C₂₆ alkyl. R² may be optionallyhydroxylated C₂-C₂₅ alkyl or C₂-C₂₅ alkenyl. R³ may be H, or:

R⁴ may be a bond, or optionally hydroxylated C₁-C₂₅ alkyl, C₂-C₂₅alkenyl, or C₂-C₂₅ epoxyalkyl. R⁵ may be optionally hydroxylated C₁-C₈alkyl, C₂-C₈ alkenyl, C₆-C₁₀ aryl, or C₄-C₁₀ heteroaryl. R⁶′″ maybeC₂-C₁₀ alkyl or C₂-C₁₀ cycloalkyl. R_(b) may be optionally carboxylatedC₁-C₆ alkyl, branched alkyl, or aryl. X may be O, S, or N. R⁷″ may be:

In various embodiments, a polytriglyceride-β-ketoester composition isprovided. The polytriglyceride-β-ketoester composition may include afatty acid ester. The polytriglyceride-β-ketoester composition mayinclude a β-ketoester group bonded to one of: an alkyl chain of thefatty acid ester, or a linking group, the linking group beingrepresented by:

X may be —OH, —SH, —NH₂, or NHR_(f). R_(b) may be optionally substitutedC₁-C₆ alkyl or aryl. R_(f) may be optionally hydroxylated C₁-C₆ alkyl.The linking group may be bonded to the alkyl chain of the fatty acidester via X and the β-ketoester group may be bonded via an ester moietyto R_(b). The polytriglyceride-β-ketoester composition may include oneor more of: an amide group bonded to a carbon that is alpha to a ketoneof the β-ketoester such that the polytriglyceride-β-ketoestercomposition comprises a polytriglyceride-polyamide-β-ketoestercomposition, an amine group bonded to a carbon that is beta to a ketoneof the β-ketoester such that the polytriglyceride-β-ketoestercomposition comprises a polytriglyceride-polyamino-β-ketoestercomposition an enamine group bonded to a keto-carbonyl of theβ-ketoester such that the polytriglyceride-β-ketoester compositioncomprises a polytriglyceride-polyenamine-β-ketoester composition, and ahydrazone group bonded to a keto-carbonyl of the β-ketoester such thatthe polytriglyceride-β-ketoester composition comprises apolytriglyceride-polyhydrazone-β-ketoester composition.

In some embodiments, polytriglyceride-β-ketoester composition mayinclude one or more of the polytriglyceride-polyamide-β-ketoestercomposition, the polytriglyceride-polyamino-β-ketoester composition, thepolytriglyceride-polyenamine-β-ketoester composition and thepolytriglyceride-polyhydrazone-β-ketoester composition.

In several embodiments, the polytriglyceride-β-ketoester composition mayinclude the fatty acid ester and the β-ketoester group bonded to thealkyl chain of the fatty acid ester. The polytriglyceride-β-ketoestercomposition may include the amide group bonded to the carbon of thealkyl chain that is alpha to the ketone of the β-ketoester such that thepolytriglyceride-β-ketoester composition may include thepolytriglyceride-polyamide-β-ketoester composition. Thepolytriglyceride-β-ketoester composition may include the amine groupbonded to the carbon of the alkyl chain that is beta to the ketone ofthe β-ketoester such that the polytriglyceride-β-ketoester compositionmay include the polytriglyceride-polyamino-β-ketoester composition. Thepolytriglyceride-β-ketoester composition may include the hydrazine groupbonded to the keto-carbon of the β-ketoester such that thepolytriglyceride-β-ketoester composition may include thepolytriglyceride-polyhydrazone-β-ketoester composition.

In some embodiments, the polytriglyceride-β-ketoester composition mayinclude one or more of the polytriglyceride-polyamide-β-ketoestercomposition, the polytriglyceride-polyamino-β-ketoester composition, andthe polytriglyceride-polyhydrazone-β-ketoester composition.

In some embodiments, the polytriglyceride-β-ketoester composition may bein the form of one or more of: a cross-linked coating and a cross-linkedfoam. The polytriglyceride-β-ketoester composition may be in the form ofa cross-linked coating on a surface. The polytriglyceride-β-ketoestercomposition may be in the form of a cross-linked coating on a metalsurface. The polytriglyceride-β-ketoester composition may be in the formof a cross-linked coating on an interior surface of a beverage or foodcontainer. The surface may include a foil or metal packaging material.The surface may include one or more of: low carbon steel, aluminum,anodized aluminum, silver, and alloys or mixtures thereof. The surfacemay be one or more of an interior surface or an exterior surface of amedical device. The polytriglyceride-β-ketoester composition may form across-linked coating on one or more of the interior surface and theexterior surface of the medical device. Further, silver may be includedby one or more of: the interior surface, the exterior surface, and thepolytriglyceride-β-ketoester composition forming the cross-linkedcoating. The silver may be in ionic or oxide form.

In several embodiments, the triglyceride polyamido-β-ketoestercomposition may include the fatty acid ester. The triglyceridepolyamido-β-ketoester composition may include the β-ketoester groupbonded to one of: the alkyl chain of the fatty acid ester, or thelinking group. The triglyceride polyamido-β-ketoester composition mayinclude the amide group bonded to a carbon of the alkyl chain that maybe alpha to a ketone of the β-ketoester. For example, the triglyceridepolyamido-β-ketoester composition may be represented by Formula XI:

Each R^(1-XI) independently may be H,

provided that at least one R^(1-XI) may be:

R²′ may be optionally hydroxylated C₂-C₂₆ alkyl. R² may be optionallyhydroxylated C₂-C₂₅ alkyl or optionally hydroxylated C₂-C₂₅ alkenyl. R³may be H, or:

R⁴ may be a bond, optionally hydroxylated C₁-C₂₅ alkyl, optionallyhydroxylated C₂-C₂₅ alkenyl, or optionally hydroxylated C₂-C₂₅epoxyalkyl. R⁵ may be optionally hydroxylated C₁-C₈ alkyl, optionallyhydroxylated C₂-C₈ alkenyl, optionally hydroxylated C₆-C₁₀ aryl, oroptionally hydroxylated C₄-C₁₀ heteroaryl. R⁶ may be C₂-C₆ alkyl, C₆-C₁₀aryl, C₁-C₆ alkyl-C₆-C₁₀ aryl, C₃-C₅ heteroaryl, or C₁-C₆ alkyl-C₃-C₅heteroaryl. R_(b) may be optionally carboxylated C₁-C₆ alkyl, branchedalkyl, or aryl. X may be O, S, or N. R⁷ may be:

In several embodiments, the triglyceride polyamido-β-ketoestercomposition may be represented by Formula XV:

At least one R^(1-XV) may be:

R²′ may be optionally hydroxylated C₂-C₂₆ alkyl. R² may be optionallyhydroxylated C₂-C₂₅ alkyl or optionally hydroxylated C₂-C₂₅ alkenyl. R³may be H, or:

R⁴ may be a bond, optionally hydroxylated C₁-C₂₅ alkyl, optionallyhydroxylated C₂-C₂₅ alkenyl, or optionally hydroxylated C₂-C₂₅epoxyalkyl. R⁵ may be optionally hydroxylated C₁-C₈ alkyl, optionallyhydroxylated C₂-C₈ alkenyl, optionally hydroxylated C₆-C₁₀ aryl, oroptionally hydroxylated C₄-C₁₀) heteroaryl.

In several embodiments, the triglyceride polyamido-β-ketoestercomposition may be represented by Formula XVI:

At least one R^(1-XVI) may be:

R² may be optionally hydroxylated C₂-C₂₅ alkyl or optionallyhydroxylated C₂-C₂₅ alkenyl. R³ may be H, or:

R⁴ may be a bond, optionally hydroxylated C₁-C₂₅ alkyl, optionallyhydroxylated C₂-C₂₅ alkenyl, or optionally hydroxylated C₂-C₂₅epoxyalkyl. R⁵ may be optionally hydroxylated C₁-C₈ alkyl, optionallyhydroxylated C₂-C₈ alkenyl, optionally hydroxylated C₆-C₁₀ aryl, oroptionally hydroxylated C₄-C₁₀ heteroaryl. R^(7a) may be:

In several embodiments, the triglyceride polyamino-β-ketoestercomposition may include the fatty acid ester. The triglyceridepolyamino-β-ketoester composition may include the β-ketoester groupbonded to one of, the alkyl chain of the fatty acid ester, or thelinking group. The triglyceride polyamino-β-ketoester composition mayinclude the amine group bonded to the carbon that may be beta to theketone of the β-ketoester. For example, the triglyceridepolyamino-β-ketoester may be represented by Formula XII:

Each R^(1-XII) may independently be H,

provided that at least one R^(1-XII) may be:

R²′ may be optionally hydroxylated C₂-C₂₆ alkyl. R² may be optionallyhydroxylated C₂-C₂₅ alkyl or optionally hydroxylated C₂-C₂₅ alkenyl. R³may be H, or:

R⁴ may be a bond, optionally hydroxylated C₁-C₂₅ alkyl, optionallyhydroxylated C₂-C₂₅ alkenyl, or optionally hydroxylated C₂-C₂₅epoxyalkyl. R⁵ may be optionally hydroxylated C₁-C₈ alkyl, optionallyhydroxylated C₂-C₈ alkenyl, optionally hydroxylated C₆-C₁₀ aryl, oroptionally hydroxylated C₄-C₁₀ heteroaryl. R⁶′ may be C₂-C₆ alkyl,C₆-C₁₀ aryl, C₁-C₆ alkyl-C₆-C₁₀ aryl. C₃-C₅ heteroaryl, or C₁-C₆alkyl-C₃-C₅ heteroaryl. R_(b) may be optionally carboxylated C₁-C₆alkyl, branched alkyl, or aryl. X may be O, S, or N. R⁶″ may be: CH₂OH,CH₂OCH₃, CH₂SH, CH₂SCH₃,

R⁷′ may be:

In some embodiments, the triglyceride polyamino-β-ketoester compositionmay be represented by Formula XVII:

At least one R^(1-XVII) may be:

R² may be optionally hydroxylated C₂-C₂₅ alkyl or optionallyhydroxylated C₂-C₂₅ alkenyl. R³ may be H, or:

R⁴ may be a bond, optionally hydroxylated C₁-C₂₅ alkyl, optionallyhydroxylated C₂-C₂₅ alkenyl, or optionally hydroxylated C₂-C₂₅epoxyalkyl. R⁵ may be optionally hydroxylated C₁-C₈ alkyl, optionallyhydroxylated C₂-C₈ alkenyl, optionally hydroxylated C₆-C₁₀ aryl, oroptionally hydroxylated C₄-C₁₀ heteroaryl. R^(7b) may be OH, OCH₃, SH,SCH₃,

In several embodiments, the polytriglyceride-β-ketoester may include thefatty acid ester. The polytriglyceride-β-ketoester may include theβ-ketoester bonded to one of: the alkyl chain of the fatty acid ester,or the linking group. The polytriglyceride-β-ketoester may include theenamine group bonded to the keto-carbon of the β-ketoester such that thepolytriglyceride-β-ketoester composition may include thepolytriglyceride polyenamine-β-composition. For example, thepolytriglyceride polyenamine-β-composition may be represented by:

Each R^(1-XIII) may independently be H,

provided that at least one R^(1-XIII) may be:

R²′ may be optionally hydroxylated C₂-C₂₆ alkyl. R² may be optionallyhydroxylated C₂-C₂₅ alkyl or C₂-C₂₅ alkenyl. R³ may be H, or:

R⁴ may be a bond, or optionally hydroxylated C₁-C₂₅ alkyl, C₂-C₂₅alkenyl, or C₂-C₂₅ epoxyalkyl. R⁵ may be optionally hydroxylated C₁-C₈alkyl, C₂-C₈ alkenyl, C₆-C₁₀ aryl, or C₄-C₁₀ heteroaryl. R⁶′″ may beC₂-C₁₀ alkyl or C₂-C₁₀ cycloalkyl. R_(b) may be optionally carboxylatedC₁-C₆ alkyl, branched alkyl, or aryl. X may be O, S, or N. R⁷″ may be:

In some embodiments, the triglyceride polyhydrazone-β-ketoester mayinclude the fatty acid ester. The triglyceride polyhydrazone-β-ketoestermay include the β-ketoester group bonded to one of: the alkyl chain ofthe fatty acid ester, or the linking group. The triglyceridepolyhydrazone-β-ketoester may include the hydrazone group bonded to theketo-carbon of the β-ketoester. For example, the triglyceridepolyhydrazone-β-ketoester may be represented by Formula XVIII

Each R^(1-XVIII) may independently be H or:

provided that at least one R^(1-XIII) may be:

R²′ may be optionally hydroxylated C₂-C₂₆ alkyl. R² may be optionallyhydroxylated C₂-C₂₅ alkyl or optionally hydroxylated C₂-C₂₅ alkenyl. R³may be H, or:

R⁴ may be a bond, optionally hydroxylated C₁-C₂₅ alkyl, optionallyhydroxylated C₂-C₂₅ alkenyl, or optionally hydroxylated C₂-C₂₅epoxyalkyl. R⁵ may be optionally hydroxylated C₁-C₈ alkyl, optionallyhydroxylated C₂-C₈ alkenyl, optionally hydroxylated C₆-C₁₀ aryl, oroptionally hydroxylated C₄-C₁₀ heteroaryl. R⁶′″ may be C₂-C₆ alkyl,C₄-C₁₀ carbonylalkyl, a C₄-C₁₀ sulfonylalkyl. C₆-C₁₀ aryl, C₁-C₆alkyl-C₆-C₁₀ aryl, C₃-C₅ heteroaryl, or C₁-C₆ alkyl-C₃-C₅ heteroaryl.R_(b) may be optionally carboxylated C₁-C₆ alkyl, branched alkyl, oraryl. X may be O, S, or N. R⁷″ may be:

In several embodiments, the polytriglyceride-β-ketoester composition maybe formed by any of the methods described herein for forming thepolytriglyceride-β-ketoester composition.

In various embodiments, an article including a surface coated with apolytriglyceride-β-ketoester composition is provided. Thepolytriglyceride-β-ketoester composition may be anypolytriglyceride-β-ketoester composition described herein. Thepolytriglyceride-β-ketoester composition may be formed by any of themethods described herein for forming the polytriglyceride-β-ketoestercomposition. The surface may be a metal surface. The article may be abeverage or food container. The polytriglyceride-β-ketoester compositionmay form a coating on an interior surface of the beverage or foodcontainer. The surface may include a foil or metal packaging material.The surface may include one or more of: low carbon steel, aluminum,anodized aluminum, silver, and alloys or mixtures thereof. The surfacemay be one or more of an interior surface or an exterior surface of amedical device. The polytriglyceride-β-ketoester composition may formacross-linked coating on one or more of the interior surface and theexterior surface of the medical device. Further, silver may be includedby one or more of: the interior surface, the exterior surface, and thepolytriglyceride-β-ketoester composition forming the cross-linkedcoating. The silver may be in ionic or oxide form. The article may beformed with the surface coated with the polytriglyceride-β-ketoestercomposition by any of the methods described herein for forming thepolytriglyceride-β-ketoester composition.

In various embodiments, a method for preparing a β-ketoimide compositionis provided. The method may include: contacting a primary amine with aβ-ketoester to form a reaction mixture; and allowing the primary amineand the β-ketoester to react effective to form the β-ketoimide.

In some embodiments, the method may include removing an alcoholbyproduct from the reaction mixture by one of: distillation, contactwith a molecular sieve, and reduced pressure. The method may includeallowing the primary amine and the β-ketoester to react at a temperaturein ° C. of at least about one or more of: 140, 150, 160.170, 180, 190,and 200. The method may include allowing the primary amine and theβ-ketoester to react for a period of time in minutes of at least aboutone or ore of 30, 60, 90, 120, 150, 180, 210, 240, 270, 300, 330, 360,390 and 420. The method may include removing one or more of an unreactedprimary amine and an unreacted β-ketoester from the reaction mixture byone of: distillation and reduced pressure. The β-ketoester may berepresented by Formula XIV:

R″ may be methyl, ethyl, t-butyl, or phenyl. R may be optionallyhydroxylated C₁-C₈ alkyl, optionally hydroxylated C₂-C₈ alkenyl,optionally hydroxylated C₆-C₁₀ aryl, or optionally hydroxylated C₄-C₁₀heteroaryl. R⁸ may be H, optionally hydroxylated C₁-C₈ alkyl, oroptionally hydroxylated C₆-C₁₀ aryl.

In some embodiments, the β-ketoimide composition may be represented byFormula XIX.

R⁵ may be optionally hydroxylated C₁-C₈ alkyl, optionally hydroxylatedC₂-C₈ alkenyl, optionally hydroxylated C₆-C₁₀ aryl, or optionallyhydroxylated C₄-C₁₀ heteroaryl. R⁸ may be H, C₁-C₈ alkyl, or C₆-C₁₀aryl. R⁹ may be C₁-C₈ alkyl or C₆ aryl optionally substituted with oneor more of: nitro, carbonyl, haloalkyl, and halogen. The primary aminemay be a diamine.

In several embodiments, the β-ketoimide composition may be representedby Formula VII:

R⁵ may be optionally hydroxylated C₁-C₈ alkyl, optionally hydroxylatedC₂-C₈ alkenyl, optionally hydroxylated C₆-C₁₀ aryl, or optionallyhydroxylated C₄-C₁₀ heteroaryl. R¹⁰ may be C₂-C₆ alkyl, C₃-C₅heteroaryl, or C₆ aryl optionally substituted with one or more of:nitro, carbonyl, haloalkyl, and halogen.

In various embodiments, a β-ketoimide composition is provided. Theketoimide composition may include at least one tertiary β-ketoimide. Forexample, the β-ketoimide composition may be represented by Formula XIX:

R⁵ may be optionally hydroxylated C₁-C₈ alkyl, optionally hydroxylatedC₂-C₈ alkenyl, optionally hydroxylated C₆-C₁₀ aryl, or optionallyhydroxylated C₄-C₁₀ heteroaryl. R⁸ may be H, C₁-C₈ alkyl, or C₆-C₁₀aryl. R⁹ may be C₁-C₈ alkyl or C₆ aryl optionally substituted with oneor more of: nitro, carbonyl, haloalkyl, and halogen. For example, theβ-ketoimide composition may be represented by Formula XII:

R⁵ may be optionally hydroxylated C₁-C₈ alkyl, optionally hydroxylatedC₂-C₈ alkenyl, optionally hydroxylated C₆-C₁₀ aryl, or optionallyhydroxylated C₄-C₁₀ heteroaryl. R¹⁰ may be C₂-C₆ alkyl, C₃-C₅heteroaryl, or C₆ aryl optionally substituted with one or more of:nitro, carbonyl, haloalkyl, and halogen.

In several embodiments, the β-ketoimide composition may be representedby Formula XVI:

In some embodiments, the the β-ketoimide composition may be representedby Formula XVII:

R⁵ may be optionally hydroxylated C₁-C₈ alkyl, optionally hydroxylatedC₂-C₈ alkenyl, optionally hydroxylated C₆-C₁₀ aryl, or optionallyhydroxylated C₄-C₁₀ heteroaryl.

In various embodiments, a method for preparing a AAG composition isprovided. The method may include providing a poly-functional compoundincluding two or more functional groups. Each functional group mayindependently be hydroxy, amino, or alkenyl. The method may includereacting the poly-functional compound under conditions effective to formthe AAG composition by one or more of the following. For example, themethod may include reacting the poly-functional compound underconditions effective to form the AAG composition by contacting thepoly-functional compound with a ketene compound, wherein thepoly-functional compound includes at least one hydroxy group. The methodmay include reacting the poly-functional compound under conditionseffective to form the AAG composition by contacting the poly-functionalcompound with a β-ketoester, wherein the poly-functional compoundincludes at least one hydroxy or amino group. The method may includereacting the poly-functional compound under conditions effective to formthe AAG composition by contacting the poly-functional compound with aperoxo reagent and one or more of: a β-ketoimide, a β-ketoester, and aβ-ketoacid, wherein the poly-functional compound includes at least onealkenyl group. The method may include reacting the poly-functionalcompound under conditions effective to form the AAG composition bycontacting the poly-functional compound with a mercaptoalkanol in thepresence of an initiator effective to form a mercaptoalkanol-substitutedcompound. The poly-functional compound may include at least one alkenylgroup. The method may include further reacting themercaptoalkanol-substituted compound with one or more of: theβ-ketoester and the β-ketoacid effective to form the AAG composition.

In some embodiments, the poly-functional compound is a natural oilderived from any organism, for example, plants, mammals, reptiles, fish,mollusks, crustaceans, fungi, algae, diatoms, and the like. In someembodiments, the poly-functional compound may exclude triglyceridesderived from oil of one or more of: legume seeds, non-legume seeds, andterrestrial animal fat. In some embodiments, the poly-functionalcompound may include triglyceride-derived oils from marine,non-terrestrial plant and animal sources, e.g., marine plants (e.g.,water hyacinth), marine mammals, marine reptiles, fish, mollusks,crustaceans, marine microorganisms (e.g., fungi, bacteria, algae,diatoms), and the like, or in some embodiments, marine sources such asmarine plants (e.g., water hyacinth), marine mammals, marine reptiles,fish, mollusks, crustaceans, marine microorganisms (e.g., fungi,bacteria, algae, diatoms), and the like. In some embodiments, thepoly-functional compound may exclude triglyceride-derived oils from anysource.

In several embodiments, the method may be conducted substantially in theabsence of solvent.

The method may include contacting the poly-functional compound with thei-ketoester to form a reaction mixture. The poly-functional compound mayinclude one or more of the hydroxyl group; and the amino group. Themethod may include allowing the poly-functional compound and theβ-ketoester to react substantially in the absence of solvent effectiveto form the AAG composition.

For example, the polyfunctional compound may be a polyol and thecorresponding AAG composition may be a polyol-AAG composition. Thepolyfunctional compound may be a polyamine and the corresponding AAGcomposition may be a polyamine-AAG composition. The polyfunctionalcompound may be a polyol-polyamine and the corresponding AAG compositionmay be a polyol-polyamine-AAG composition.

In some embodiments, the method may include removing an alcoholbyproduct from by one or more of: distillation, reduced pressure, andcontact with a molecular sieve. The method may include reacting thepoly-functional compound, e.g., with the β-ketoester, under an inertatmosphere. The method may include allowing the polyfunctional compoundto react, e.g., with the β-ketoester, at a temperature in ° C. of atleast about one or more of: 120.130, 140, 150, 160, 170, 180, 190, and200, or a range between any two of the preceding values, for example,between about 120 and about 200. The method may include allowing thepoly-functional compound to react, e.g., with the β-ketoester, for aperiod of time in hours of at least about one or more of: 0.25, 0.5, 1,2, 3, 4, 56, 7, 0.8, 9, 10, 15, 20, and 24, or a range between any twoof the preceding values, for example, between about 0.25 and about 24.

In several embodiments, at least a portion of the poly-functionalcompound may be a polyol derived from a pyrolyzed bio-oil. The pyrolyzedbio-oil may be derived from pyrolysis of one or more of: hardwood,softwood, grass, reeds, bagasse, sugarcane, corn stover, and sorghum. Atleast a portion of the poly-functional compound may be a polyol derivedfrom alkoxylated pyrolyzed bio-oil. At least a portion of thepoly-functional compound may include one or more of a phenol, a cresol,a guaiacol, and a syringol. At least a portion of the poly-functionalcompound may include one or more of: pyrogallol, catechol, resorcinol,hydroquinone, lignin, and diphenolic acid. In some embodiments, at leasta portion of the poly-functional may include an unsaturatednon-triglyceride oil derived from a marine organism, a mammal, and aninsect. The marine organism may include, for example one or more of:algae, water hyacinth, bacteria, and diatoms. The poly-functionalcompound may include lignin or derivatives thereof. The poly-functionalcompound may be derived from a petroleum source. For example thepoly-functional compound may include a petroleum derived polyol, apetroleum-derived polyamine, a petroleum-derived polyalkene, or acomposite or combination thereof. In some embodiments, thepoly-functional compound may be derived from a natural source, such as anatural oil as described herein, e.g., in some embodiments, a naturaloil excluding a triglyceride. In several embodiments, thepoly-functional compound may exclude compounds derived from a petroleumsource.

The poly-functional compound may be a polyol and the AAG may be apolyol-AAG. The poly-functional compound may include a C₂-C₂₀ compoundsubstituted with at least one hydroxyl group. At least a portion of thepoly-functional compound may be a polyol derived from ahydroxyl-containing fatty acid ester.

In some embodiments, at least a portion of the poly-functional compoundmay be a polyol derived from one or more of: a hydroxyl-containingtriglyceride and a hydroxyl-containing fatty acid ester. At least aportion of the poly-functional compound may be represented by FormulaXX:

Each R^(1-XX) may independently be:

provided that at least one R^(1-XX) may be:

R²′ may be C₂-C₂₆ alkyl, optionally substituted with —OH or —NH₂. R² maybe C₂-C₂₅ alkyl or C₂-C₂₅ alkenyl, optionally substituted with —OH or—NH₂. R⁴ may be a bond, or C₁-C₂₅ alkyl, C₂-C₂₅ alkenyl, or C₂-C₂₅epoxyalkyl, optionally substituted with —OH or —NH₂. R⁴′ may be a bond;or C₁-C₂₅ alkyl, C₂-C₂₅ alkenyl, or C₂-C₂₅ epoxyalkyl, optionallysubstituted with —OH or —NH₂. R¹¹ may be C₂-C₁₂ alkyl, C₆-C₁₂ aryl, orC₂-C₁₂ alkyl-C₆-C₁₂ aryl. X may be —O—, —S—, or —NH—.

In several embodiments, at least a portion of the polyol represented byFormula XX may be derived from an unsaturated triglyceride. Theunsaturated triglyceride may be modified by an electrophilic addition ofone or more of: a C₂-C₁₂ diol, a C₂-C₁₂alkanol amine, and a C₂-C₁₂diamine to an alkene of the unsaturated fatty acid ester.

In various embodiments, the ketene compound may include one or more of:4-methyleneoxetan-2-one, 4-ethylidene-3-methyloxetan-2-one, and4-benzylidene-3-phenyloxetane-2-one. The ketene compound may be derivedfrom one or more of: an α-diazo ketone and an α-halo acyl halide. Theketene compound may be optionally substituted with one or more of: C₁-C₈alkyl and C₆-C₁₀ aryl.

In various embodiments, the β-ketoester may be represented by FormulaXIV:

R″ may be C₁-C₈ alkyl or C₆-C₁₀ aryl. R⁵ may be C₁-C₈ alkyl, C₂-C₈alkenyl, C₆-C₁₀ aryl, or C₄-C₈ heteroaryl, optionally substituted with—OH or —NH₂. R⁸ may be H, C₁-C₈ alkyl, or C₆-C₁₀ aryl.

In several embodiments, the peroxo reagent may include one or more of:hydrogen peroxide, manganese dioxide, sodium percarbonate, potassiumpercarbonate, sodium perborate, potassium perborate, and the like.

In some embodiments, the β-ketoimide may be represented by Formula VI:

R⁵ may be optionally hydroxylated C₁-C₈ alkyl, C₂-C₈ alkenyl C₆-C₁₀aryl, or C₁-C₈ heteroaryl; and R⁹ may be C₁-C₈ alkyl or C₆ aryloptionally substituted with one or more of: nitro, carbonyl, haloalkyl,and halogen.

In various embodiments, the β-ketoimide may be represented by FormulaVII:

R⁵ may be optionally hydroxylated C₁-C₈ alkyl, C₂-C₈ alkenyl, C₆-C₁₀aryl, or C₄-C₈ heteroaryl; and R¹⁰ may be a C₂-C₆ alkyl, C₃-C₅heteroaryl, or C₆ aryl optionally substituted with one or more of:nitro, carbonyl, halogen, and haloalkyl.

In some embodiments, the β-ketoimide may be represented by Formula VIII:

In several embodiments, the β-ketoimide may be represented by FormulaVIV:

R⁵ may be optionally hydroxylated C₁-C₈ alkyl, C₂-C₈ alkenyl. C₆-C₁₀aryl, or C₄-C₈ heteroaryl.

In various embodiments, the β-ketoacid may be represented by FormulaIII:

R⁵ may be optionally hydroxylated C₁-C₈ alkyl, C₂-C₈ alkenyl, C₆-C₁₀aryl, or C₄-C₁₀ heteroaryl, and R⁸ may be H, or optionally hydroxylatedC₁-C₈ alkyl or C₆-C₁₀ aryl.

In some embodiments, the β-ketoacid may include one or more of:3-oxobutanoic acid, 3-oxopentanoic acid, 3-oxohexanoic acid,3-oxo-3-phenylpropanoic acid, and the like.

In some examples, the mercaptoalkanol may be: e.g., a C₁-C₈mercaptoalkanol, for example, the mercaptoalkanol may include one ormore of: thioglycerol and mercaptoethanol.

In some embodiments, the AAG composition may include a compoundrepresented by Formula XXI:

Each R^(1-XXI) may independently be:

provided that at least one R^(1-XXI) may be:

R^(2′) may be C₂-C₂₆ alkyl, optionally substituted with —OH or —NH₂. R²may be C₂-C₂₅ alkyl or C₂-C₂₅ alkenyl, optionally substituted with —OHor —NH₂. R⁴ may be a bond, or C₁-C₂₅ alkyl, C₂-C₂₅ alkenyl, or C₂-C₂₅epoxyalkyl, optionally substituted with —OH or —NH₂. R⁴′ may be a bond;or C₁-C₂₅ alkyl, C₂-C₂₅ alkenyl, or C₂-C₂₅ epoxyalkyl, optionallysubstituted with —OH or —NH₂. R⁵ may be C₁-C₈ alkyl, C₂-C₈ alkenyl.C₆-C₁₀ aryl or C₄-C₈ heteroaryl, optionally substituted with —OH or—NH₂. R¹¹ may be C₂-C₁₂ alkyl, C₆-C₁₂ aryl, or C₂-C₁₂ alkyl-C₆-C₁₂ aryl.X may be —O—, —S—, or —NH—.

In various embodiments, a method for preparing a polyol-AAG compositionis provided. The method may include contacting the poly-functionalcompound in the form of an unsaturated polyol with the peroxo reagentand the β-ketoimide to form a reaction mixture. The method may includeallowing the unsaturated polyol, the peroxo reagent, and the β-ketoimideto react effective to form the AAG composition as a polyol-AAGcomposition.

In some embodiments, the method may include pre-mixing the peroxoreagent and the β-ketoimide prior to contacting the unsaturated polyol.The method may include. The method may include pre-mixing the peroxoreagent and the β-ketoimide at a temperature less than about 25° C. Themethod may include pre-mixing the unsaturated polyol and the β-ketoimideprior to contacting the peroxo reagent. The method may include allowingthe unsaturated polyol, the peroxo reagent, and the β-ketoimide to reactat a temperature in ° C. of at least about one or more of: 0, 10, 20,30, 40, 50, 60, 70, 80, 90, and 100, or a range between any two of thepreceding values, for example, between about 0 and about 100. The methodmay include allowing the unsaturated polyol, the peroxo reagent, and theβ-ketoimide to react for a period of time in minutes of at least aboutone or more of: 5, 10, 15, 20, 30, 40, 60, 90, 120, 150, 170, and 20),or a range between any two of the preceding values, for example, betweenabout S and about 200.

In several embodiments, the method may include, after forming thepolyol-AAG composition, contacting the reaction mixture with a reducingagent effective to consume at least a portion of remaining peroxoreagent. Suitable reducing reagents may include, for example, sodiumsulfite, sodium thiosulfate, and the like. The method may include, afterforming the polyol-AAG composition, purifying the polyol-AAG compositionby one or more of: contacting the reaction mixture with one of: water,aqueous brine, and aqueous mild acid; separating an aqueous layer fromthe reaction mixture; contacting the reaction mixture to achromatography solid phase, and eluting the polyol-AAG composition fromthe chromatography solid phase to provide the polyol-AAG composition inat least partly purified form.

In various embodiments, at least a portion of the unsaturated polyol maybe derived from pyrolysis bio-oil. The pyrolysis bio-oil may be derivedfrom pyrolysis of one or more of, hardwood, softwood, grass, reeds,bagasse, corn stover, sugarcane, and sorghum. At least a portion of theunsaturated polyol may include an unsaturated triglyceride derived froma marine organism. The marine organism may include one or more of:algae, water hyacinth, bacteria, and diatoms. The algae, water hyacinth,bacteria, and diatoms may be cultured, and/or may be harvested from theocean. The unsaturated triglyceride may include an unsaturatedalkyl-diacylglycerol.

In some embodiments, the β-ketoimide may be represented by Formula VI:

R⁵ may be optionally hydroxylated: C₁-C₈alkyl, C₂-C₈ alkenyl, C₆-C₁₀aryl, or C₄-C₈ heteroaryl. R⁹ may be C₁-C₆ alkyl or C₆ aryl optionallysubstituted with one or more of: nitro, carbonyl, haloalkyl, andhalogen. The β-ketoimide may be represented by Formula VII:

R⁵ may be optionally hydroxylated C₁-C₈ alkyl, C₂-C₈ alkenyl C₆-C₁₀aryl, or C₄-C₈ heteroaryl. R¹⁰ may be a C₂-C₆ alkyl, C₃-C₅ heteroaryl,or C₆ aryl optionally substituted with one or more of: nitro, carbonyl,halogen, and haloalkyl. The β-ketoimide may be represented by FormulaVIII:

The β-ketoimide may be represented by Formula VIV:

R⁵ may be optionally hydroxylated: C₁-C₈ alkyl C₂-C₈ alkenyl, C₆-C₁₀aryl or C₄-C₈ heteroaryl.

In several embodiments, the peroxo reagent may include one or more ofthydrogen peroxide, manganese dioxide, sodium percarbonate, potassiumpercarbonate, sodium perborate, potassium perborate, and the like.

In various embodiments of the method, the polyol-AAG composition mayinclude: a polyol unit, at least one hydroxyl group bonded to an alkylchain of the polyol unit; and a β-ketoester group bonded to a carbonatom of the alkyl chain that may be alpha to a carbon atom bearing thehydroxyl group. The polyol-AAG composition may include a hydroxyl valuegreater than the unsaturated polyol.

In various embodiments, a method for preparing a poly(AAG)-compositionis provided. The method may include contacting an AAG composition, e.g.,any AAG composition described herein, with a cross-linking compound toform a reaction mixture. The method may include allowing the AAGcomposition and the cross-linking compound to react effective to formthe poly(AAG) composition. In some embodiments, the AAG composition maybe any AAG composition described herein. In some embodiments, the AAGcomposition may be any AAG composition described herein, provided thatthe AAG composition is not a triglyceride-AAG composition.

The method may include contacting the AAG composition with thecross-linking compound to form the reaction mixture, the AAG compositionbeing, for example, a AAG-β-ketoester composition. The method mayinclude allowing the AAG composition and the cross-linking compound toreact effective to form the AAG composition as, for example, apoly(AAG)-β-ketoester composition.

In some embodiments, the AAG composition may be derived from pyrolyzedbio-oil. The pyrolyzed bio-oil may be derived from pyrolysis of one ormore of: hardwood, softwood, grass, reeds, bagasse, corn stover,sugarcane, and sorghum. The AAG composition may be derived from one ormore of, a phenol, a cresol, a guaiacol, and a syringol. The AAGcomposition may be derived from an alkoxylated pyrolyzed bio-oil. TheAAG composition may be derived from a hydroxyl-containing fatty acidester.

In several embodiments, the AAG composition may be derived from ahydroxyl-containing triglyceride. For example, the polyol-AAGcomposition may include a compound represented by Formula XX:

Each R^(1-XX) may independently be:

provided that at least one R^(1-XX) may be:

R²′ may be C₂-C₂₆ alkyl, optionally substituted with —OH or —NH₂. R₂ maybe C₂-C₂₅ alkyl or C₂-C₂₅ alkenyl, optionally substituted with —OH or—NH₂. R⁴ may be a bond, or C₁-C₂₅ alkyl, C₂-C₂₅ alkenyl, or C₂-C₂₅epoxyalkyl, optionally substituted with —OH or —NH₂. R⁴′ may be a bond;or C₁-C₂₅ alkyl, C₂-C₂₅ alkenyl, or C₂-C₂₅ epoxyalkyl, optionallysubstituted with —OH or —NH₂. R¹¹ may be C₂-C₂₅ alkyl, C₆-C₁₂ aryl, orC₂-C₁₂alkyl-C₆-C₁₂ aryl. X may be —O—, —S—, or —NH—. The compoundrepresented by Formula XX may be derived from an unsaturatedtriglyceride modified by an electrophilic addition of one or more of: aC₂-C₁₂ diol, a C₂-C₁₂ alkanol amine, and a C₂-C₁₂ diamine to an alkeneof the unsaturated fatty acid ester.

In various embodiments, the method may include contacting the AAGcomposition with the cross-linking compound in the presence of asurfactant. The method may include allowing the AAG composition and thecross-linking compound to react at a temperature in ° C. of at leastabout one or more of: 140, 150, 160, 170, 180, 190, and 200, or a rangebetween any two of the preceding values, for example, between about 140and about 200. The method may include allowing the AAG composition andthe cross-linking compound to react for a period of time in minutes ofat least about one or more of: 5, 10, 15, 20, 25, 30, 35, 40, 45, 50,55, and 60, or a range between any two of the preceding values, forexample, between about 5 and about 60. The method may include contactingthe AAG composition with the cross-linking compound in the presence ofone or more of: an inert atmosphere; water; a blowing agent; and a base.The base may include one or more of: magnesium hydroxide, zirconiumhydroxide, aluminum hydroxide, and the like.

In some embodiments, the method may include applying the reactionmixture to a surface. The method may include heating the reactionmixture and the surface effective to form the poly(AAG)-composition,e.g., the poly(AAG)-β-ketoester composition, as a cross-linked coatingon the surface. The method may include contacting the AAG compositionand the cross-linking compound to form the reaction mixture at about 25°C. for less than 3 minutes. The method may include applying the reactionmixture onto the surface. The method may include heating the reactionmixture and the surface at a temperature of about 180° C. for 30 minuteseffective to form the poly(AAG)-composition, e.g., thepoly(AAG)-β-ketoester composition, as a cross-linked coating on thesurface. The surface may be a metal surface. The surface may be aninterior surface of a food or beverage container. The surface mayinclude a foil or metal packaging material. The surface may include oneor more of: low carbon steel, aluminum, anodized aluminum, silver, andalloys or mixtures thereof. The surface may be one or more of aninterior surface or an exterior surface of a medical device. Thepoly(AAG)-compositions, e.g., as a poly(AAG)-β-ketoester composition,may form a cross-linked coating on one or more of the interior surfaceand the exterior surface of the medical device. Further, silver may beincluded by one or more of: the interior surface, the exterior surface,and the poly(AAG)-composition, e.g., as the poly(AAG)-β-ketoestercomposition, forming the cross-linked coating. The silver may be inionic or oxide form.

In several embodiments, the method may include contacting the AAGcomposition and the cross-linking compound at about 25° C. The methodmay include pouring the reaction mixture into a mold, the mold coated ina mold release agent. The cross-linking compound may include one or moreof a diisocyanate, a triisocyanate, and a tetraisocyanate. Thecross-linking compound may include a polymer including more than oneisocyanate group. The cross-linking compound may include one or moreisocyanate cross-linking reagents, e.g.: Luprinate M20, PMDI, DesmodurDA-L, Desmodur DN, Bayhydur 302, VESTANAT® T, VESTANAT® HB, VESTANAT®HT, VESTANAT® B, VESTANAT® DS, and like isocyanate cross-linkingreagents.

In various embodiments of the method, the poly(AAG)-composition, e.g.,as the poly(AAG)-β-ketoester composition, may include apolyol-polyamido-β-ketoester. The polyol-polyamido-β-ketoester mayinclude: a polyol unit; a β-ketoester group located on an alkyl chain ofthe polyol unit; and an amide group bonded to a carbon of the alkylchain that may be alpha to a ketone of the β-ketoester. Thepolyol-polyamido-β-ketoester composition may include a compoundrepresented by Formula XXII:

Each R^(1-XXII) may independently be:

provided that at least one R^(1-XXII) may be:

R²′ may be C₂-C₂₆ alkyl, optionally substituted with —OH or —NH₂. R² maybe C₂-C₂₅ alkyl or C₂-C₂₅ alkenyl, optionally substituted with —OH or—NH₂. R⁴ may be a bond, or C₁-C₂₅ alkyl, C₂-C₂₅ alkenyl, or C₂-C₂₅epoxyalkyl, optionally substituted with —OH or —NH₂. R⁴′ may be a bond;or C₁-C₂₅ alkyl, C₂-C₂₅ alkenyl, or C₂-C₂₅ epoxyalkyl, optionallysubstituted with —OH or —NH₂. R⁵ may be C₁-C₈ alkyl, C₂-C₈ alkenyl,C₆-C₁₀ aryl, or C₄-C₈ heteroaryl, optionally substituted with —OH or—NH₂. R¹¹ may be C₂-C₁₂ alkyl, C₆-C₁₂ aryl, C₁-C₆ alkyl-C₆-C₁₀ aryl,C₃-C₅ X may be —O—, —S—, or —NH—. R¹² may be C₂-C₆ alkyl, C₆-C₁₀ aryl,C₁-C₆ alkyl-C₆-C₁₀ aryl, C₃-C₅ heteroaryl, or C₁-C₆ alkyl-C₃-C₅heteroaryl. R¹³ may be:

In some embodiments, the cross-linking compound may include one or moreof: a hemiaminal, a hemiaminal ether, a hemiaminal thioether an aromatichemiaminal, an aromatic hemiaminal ether, an aromatic hemiaminalthioether, a polymer including a hemiaminal, a polymer including ahemiaminal ether, and a polymer including a hemiaminal thioether. Thecross-linking agent may include one or more hemiaminal cross-linkingreagents (e.g., the CYMEL™ series from Allnex USA, Inc., Alpharetta,Ga.), such as CYMEL™ 303, CYMEL® 300. CYMEL™ 301, CYMEL™ 303 LF, CYMEL™304, CYMEL™ 350, CYMEL™ 3745, CYMEL™ XW 3106, CYMEL™ MM-100, CYMEL™ 323,CYMEL™ 325, CYMEL™ 327, CYMEL™ 328, CYMEL™ 385, CYMEL™ 370, CYMEL™ 373,CYMEL™ 380, and the like. The method may include contacting the AAGcomposition with the cross-linking compound in the presence of an acidcatalyst. The acid catalyst may include one or more of: p-toluenesulfonic acid; methane sulfonic acid; a C₁-C₈ carboxylic acid; a C₁-C₈halocarboxylic acid, e.g., trifluoromethane sulfonic acid, chloroaceticacid, dichloroacetic acid, trichloroacetic acid, and the like: apolymeric sulfonic acid resin, and the like. The method may includecontacting the AAG composition with the cross-linking compound in thepresence of a Lewis acid catalyst, e.g., boron trifluoride. The methodmay include removing an alcohol byproduct from the reaction mixture byone or more of: distillation, reduced pressure, and contact with amolecular sieve.

In several embodiments of the method, the poly(AAG)-composition, e.g.,as the poly(AAG)-β-ketoester composition, may include a polyolpolyamino-β-ketoester. The polyol polyamino-β-ketoester may include: apolyol unit; a β-ketoester group bonded to an alkyl chain of the polyolunit, amid an amine group bonded to a carbon beta to a ketone of theβ-ketoester. The poly(AAG)-composition, e.g., as the polyolpolyamino-β-ketoester composition may include a compound represented byFormula XXIII:

Each R^(1-XXIII) may independently be:

provided that at least one R^(1-XXIII) may be:

R²′ may be C₂-C₂₆ alkyl, optionally substituted with —OH or —NH₂. R² maybe C₂-C₂₅ alkyl or C₂-C₂₅ alkenyl, optionally substituted with —OH or—NH₂, R⁴ may be a bond, or C₁-C₂₅ alkyl, C₂-C₂₅ alkenyl, or C₂-C₂₅epoxyalkyl, optionally substituted with —OH or —NH₂. R⁴′ may be a bond;or C₁-C₂₅ alkyl, C₂-C₂₅ alkenyl, or C₂-C₂₅ epoxyalkyl, optionallysubstituted with —OH or —NH₂. R⁵ may be C₁-C₈ alkyl, C₂-C₈ alkenyl,C₆-C₁₀ aryl, or C₂-C₁₂ heteroaryl, optionally substituted with —OH or—NH₂. R¹²′ may be C₂-C₁₂ alkyl, C₆-C₁₂ aryl or C₂-C₁₂ alkyl-C₆-C₁₂ aryl.X may be —O—, —S—, or —NH—. R¹²′ may be C₂-C₆ alkyl, C₆-C₁₀ aryl, C₁-C₆alkyl-C₆-C₁₀ aryl, C₃-C₅ heteroaryl, or C₁-C₆ alkyl-C₃-C₅ heteroaryl.R¹²″ may be: CH₂OH, CH₂OCH₃, CH₂SH, CH₂SCH₃,

R¹³′ may be:

In many embodiments, the crosslinking compound may include a polyamine.For example, the polyamine may include a diamine, triamine, and thelike. The polyamine may be aliphatic or cycloaliphatic. The polyaminemay be aromatic aryl, or aralkyl. The polyamine may include a mixture ofaliphatic, cycloaliphatic, and aromatic polyamines. For example, thepolyamine may include any of the ANACAMINE® series (Air Products.Allentown, Pa.), e.g., ANACAMINE® 2049, ANACAMINE® 1110, ANACAMINE®1482. ANACAMINE® 1608, ANACAMINE® 1617LV, ANACAMINE® 1638, ANACAMINE®1693, ANACAMINE® 1769, ANACAMINE® 1784. ANACAMINE® 1856, ANACAMINE®1884, ANACAMINE® 1922A, ANACAMINE® 2014FG, ANACAMINE® 2021. ANACAMINE®2072, ANACAMINE® 2074, ANACAMINE® 2089M, ANACAMINE® 2143. ANACAMINE®2280, and the like. The polyamine crosslinking agent may crosslink theAAG composition via imine or enamine linkages.

In various embodiments, the AAG composition may include a polyolpolyeneamine-β-ketoester. The polyol polyeneamine-β-ketoester mayinclude, for example, a polyol unit: a β-ketoester group bonded to analkyl chain of the polyol unit; and an enamine bonded to a keto-carbonof the β-ketoester and effective to cross-link more than one polyolunit.

The cross-linking compound may include one or more of: a dihydrazine anda dihydrazide. The cross-linking compound may include one or more of:adipic dihydrazide, sebacic dihydrazide, oxalyl dihydrazide, succinicdihydrazide, maleic dihydrazide, malic dihydrazide isophthalicdihydrazide, terephthalic dihydrazide and the like.

In several embodiments of the method, the poly(AAG)-composition. e.g.,as the poly(polyol)-β-ketoester composition, may include a polyolpolyhydrazone-β-ketoester. The polyol polyhydrazone-β-ketoester mayinclude: a polyol unit; a β-ketoester group bonded to an alkyl chain ofthe polyol unit; and a hydrazone bonded to a keto-carbon of theβ-ketoester and effective to cross-link more than one polyol unit. Thepoly(AAG)-composition. e.g., as the polyol polyhydrazone-β-ketoestercomposition, may include a compound represented by Formula XXIV:

Each R^(1-XXIV) may independently be:

provided that at least one R^(1-XXIV) may be:

R²′ may be C₂-C₂₆ alkyl, optionally substituted with —OH or —NH₂. R² maybe C₂-C₂₅ alkyl or C₂-C₂₅ alkenyl, optionally substituted with —OH or—NH₂. R⁴ may be a bond, or C₁-C₂₅ alkyl, C₂-C₂₅ alkenyl, or C₂-C₂₆epoxyalkyl, optionally substituted with —OH or —NH₂. R⁴′ may be a bond;or C₁-C₂₅ alkyl, C₂-C₂₅ alkenyl, or C₂-C₂₅ epoxyalkyl, optionallysubstituted with —OH or —NH₂. R⁵ may be C₁-C₈ alkyl, C₂-C₈ alkenyl,C₆-C₁₀ aryl, or C₄-C₈ heteroaryl, optionally substituted with —OH or—NH₂. R¹¹ may be C₂-C₁₂ alkyl, C₆-C₁₂ aryl, or C₂-C₁₂ alkyl-C₆-C₁₂ aryl.X may be —O—, —S—, or —NH—. R¹²′″ may be C₂-C₆ alkyl, C₆-C₁₀ aryl, C₁-C₆alkyl-C₆-C₁₀ aryl, C₃-C₅ heteroaryl, or C₁-C₆ alkyl-C₃-C₅ heteroaryl.R¹³″ may be:

In several embodiments of the method, the cross-linking compound mayinclude at least two diazonium groups. The diazonium groups may beeffective to cross-link two or more AAG compounds of the AAG compositionto form azo cross-links. The cross-linking compound may include analdehyde. The aldehyde may be effective to cross-link the β-ketoestersof two or more AAG compounds of the AAG composition through a methylenecross-link. For example, the aldehyde may be formaldehyde. Thecross-linking compound may include at least two α,β-unsaturatedcarbonyls. The α,β-unsaturated carbonyls may be effective to cross-linktwo or more polyol-AAG compounds of the AAG composition. Thecross-linking compound may be represented by Formula XIV:

R may be CH₂CH₂, CH₂(CH₃)CH, (CH₂CH₂OCH₂CH₂)_(n), or(CH₂(CH₃)CHOCH₂(CH₃)CH)_(n), and n may be an integer from 1 to 50.

In various embodiments, a poly(AAG)-composition is provided. Thepoly(AAG)-composition may include a polyfunctional moiety derived from apolyol unit, a polyamine unit, a polyalkene unit, or a combination orcomposite thereof. The poly(AAG)-composition may include a β-ketoestergroup bonded to an alkyl chain of the polyfunctional moiety. Thepoly(AAG)-composition may include one or more of the following. Thepoly(AAG)-composition may include an amide group bonded to a carbon ofthe alkyl chain that is alpha to a ketone of the β-ketoester such thatthe poly(AAG)-composition includes a poly(AAG)amido-β-ketoestercomposition. The poly(AAG)-composition may include an amine group bondedto a carbon on the alkyl chain that is beta to a ketone of theβ-ketoester such that the poly(AAG)-composition comprises apoly(AAG)amino-β-ketoester composition. The poly(AAG)-composition mayinclude a hydrazone group bonded to a keto-carbon of the β-ketoestergroup such that the poly(AAG)-composition comprises apoly(AAG)hydrazone-β-ketoester composition.

The poly(AAG)-composition may be prepared according to any method ofpreparing the poly(AAG)-composition described herein. Thepoly(AAG)-composition may be prepared from any AAG-composition asdescribed herein. For example, the poly(AAG)-composition may be preparedfrom a AAG-composition derived from the poly-functional compoundincluding two or more functional groups. Each functional group mayindependently be hydroxy, amino, or alkenyl. For example, thepoly(AAG)-composition may have structural features corresponding topreparation of the AAG-composition by contacting the poly-functionalcompound with the ketene compound, wherein the poly-functional compoundincludes at least one hydroxy group. The poly(AAG)-composition may havestructural features corresponding to preparation of the AAG-compositionby contacting the poly-functional compound with the β-ketoester, whereinthe poly-functional compound includes at least one hydroxy or aminogroup. The poly(AAG)-composition may have structural featurescorresponding to preparation of the AAG-composition by contacting thepoly-functional compound with a peroxo reagent and one or more of: aβ-ketoimide, a β-ketoester, and a β-ketoacid, wherein thepoly-functional compound includes at least one alkenyl group. Thepoly(AAG)-composition may have structural features corresponding topreparation of the AAG-composition by contacting the poly-functionalcompound with a mercaptoalkanol in the presence of an initiatoreffective to form a mercaptoalkanol-substituted compound, wherein thepoly-functional compound includes at least one alkenyl group: andfurther reacting the mercaptoalkanol-substituted compound with one ormore of: the β-ketoester and the β-ketoacid.

In some embodiments, the poly-functional compound is a natural oilderived from any organism, for example, plants, mammals, reptiles, fish,mollusks, crustaceans, fungi, algae, diatoms, and the like. In someembodiments, the poly-functional compound may exclude triglyceridesderived from oil of one or more of: legume seeds, non-legume seeds, andterrestrial animal fat. In some embodiments, the poly-functionalcompound may include triglyceride-derived oils from marine,non-terrestrial plant and animal sources, e.g., marine plants (e.g.,water hyacinth), marine mammals, marine reptiles, fish, mollusks,crustaceans, marine microorganisms (e.g., fungi, bacteria, algae,diatoms), and the like, or in some embodiments, marine sources such asmarine plants (e.g., water hyacinth), marine mammals, marine reptiles,fish, mollusks, crustaceans, marine microorganisms (e.g., fungi,bacteria, algae, diatoms), and the like. In some embodiments, thepoly-functional compound may exclude triglyceride-derived oils from anysource. In some embodiments, the poly(AAG)-composition may be preparedfrom a AAG-composition excluding the triglyceride AAG composition.

In some embodiments, the poly(AAG) composition, e.g., as apoly(AAG)-β-ketoester composition, e.g., poly(polyol)-β-ketoestercomposition, may include: a polyol unit a β-ketoester group bonded to analkyl chain of the polyol unit. The poly(AAG)-β-ketoester composition,e.g., poly(polyol)-β-ketoester composition, may include an amide groupbonded to a carbon of the alkyl chain that may be alpha to a ketone ofthe β-ketoester such that the poly(AAG)-β-ketoester composition, e.g.,poly(polyol)-β-ketoester composition, includes a polyolpolyamido-β-ketoester composition. The poly(polyol)-β-ketoestercomposition, e.g., poly(polyol)-β-ketoester composition, may include anamine group bonded to a carbon on the alkyl chain that may be beta to aketone of the β-ketoester such that the poly(AAG)-β-ketoestercomposition, e.g., poly(polyol)-β-ketoester composition, includes apolyol polyamino-β-ketoester composition. The poly(AAG)-β-ketoestercomposition, e.g. poly(polyol)-β-ketoester composition, may include ahydrazone group bonded to a keto-carbon of the β-ketoester group suchthat the poly(AAG)-β-ketoester composition, e.g.,poly(polyol)-β-ketoester composition, includes a polyolpolyhydrazone-β-ketoester composition.

In some embodiments, the poly(AAG)-composition, e.g., as thepoly(polyol)-β-ketoester composition, may be in the form of one or moreof: a cross-linked coating and a cross-linked foam. Thepoly(AAG)-composition. e.g., as the poly(polyol)-β-ketoestercomposition, may be in the form of a cross-linked coating on a surface.The poly(AAG)-composition, e.g., as the poly(polyol)-β-ketoestercomposition, may be in the form of a cross-linked coating on a metalsurface. The poly(AAG)-composition, e.g., as thepoly(polyol)-β-ketoester composition, may be in the form of across-linked coating on an interior surface of a beverage or foodcontainer. The surface may include a foil or metal packaging material.The surface may include one or more of: low carbon steel, aluminum,anodized aluminum, silver, and alloys or mixtures thereof. The surfacemay be one or more of an interior surface or an exterior surface of amedical device. The poly(AAG)-composition. e.g., as thepoly(polyol)-β-ketoester composition, may form a cross-linked coating onone or more of the interior surface and the exterior surface of themedical device. Further, silver may be included by one or more of: theinterior surface, the exterior surface, and the poly(AAG)-composition,e.g., as the poly(polyol)-β-ketoester composition, forming thecross-linked coating. The silver may be in ionic or oxide form.

In several embodiments, the composition may include the polyol unit; theβ-ketoester group bonded to an alkyl chain of the polyol unit; and theamide group bonded to the carbon of the alkyl chain alpha to the ketoneof the β-ketoester such that the poly(AAG)-composition, e.g., as thepoly(AAG)-β-ketoester composition, includes the polyolpolyamido-β-ketoester composition. The polyol polyamido-β-ketoestercomposition may include a compound represented by Formula XXV:

R⁵ may be C₁-C₈ alkyl, C₂-C₈ alkenyl, C₆-C₁₀ aryl, or C₄-C₈ heteroaryl,optionally substituted with —OH or —NH₂. R¹² may be C₂-C₆ alkyl, C₆-C₁₀aryl, C₁-C₆ alkyl-C₆-C₁₀ aryl, C₃-C₅ heteroaryl, or C₁-C₆ alkyl-C₃-C₅heteroaryl. R¹⁴ may be a polyol derived from one of: a pyrolyzedbio-oil, a modified triglyceride, and a triglyceride from a marineorganism. The polyol polyamido-β-ketoester composition may include acompound represented by Formula XXII:

Each R^(1-XXII) may independently be:

provided that at least one R^(1-XXII) may be:

R²′ may be C₂-C₂₆ alkyl, optionally substituted with —OH or —NH₂. R² maybe C₂-C₂₅ alkyl or C₂-C₂₅ alkenyl, optionally substituted with —OH or—NH₂. R⁴ may be a bond, or C₁-C₂₅ alkyl. C₂-C₂₅ alkenyl, or C₂-C₂₅epoxyalkyl, optionally substituted with —OH or —NH₂. R⁴′ may be a bond;or C₁₁-C₂₅ alkyl, C₂-C₂₅ alkenyl, or C₂-C₂₅ epoxyalkyl, optionallysubstituted with —OH or —NH₂. R⁵ may be C₁-C₈ alkyl, C₂-C₈ alkenyl,C₆-C₁₀ aryl, or C₄-C₈ heteroaryl, optionally substituted with —OH or—NH₂. R¹¹ may be C₂-C₆ alkyl, C₆-C₁₂ aryl, or C₂-C₁₂ alkyl-C₆-C₁₂ aryl.X may be —O—, —S—, or —NH—. R¹² may be C₂-C₆ alkyl, C₆-C₁₀ aryl, C₁-C₆alkyl-C₆-C₁₀ aryl, C₃-C₅ heteroaryl, or C₁-C₆ alkyl-C₃-C₅ heteroaryl R¹³may be:

The polyol polyamido-β-ketoester composition may include a compoundrepresented by Formula XXVI:

At least one R^(1-XXVI) may be:

R² may be C₂-C₂₅ alkyl or C₂-C₂₅ alkenyl, optionally substituted with—OH or —NH₂. R⁴′ may be a bond; or C₁-C₂₅ alkyl, C₂-C₂₅ alkenyl, orC₂-C₂₅ epoxyalkyl, optionally substituted with —OH or —NH₂. R⁵ may beC₁-C₈ alkyl, C₂-C₈ alkenyl, C₆-C₁₀ aryl, or C₄-C₈ heteroaryl, optionallysubstituted with —OH or —NH₂. R¹¹ may be C₂-C₁₂ alkyl, C₆-C₁₂ aryl, orC₂-C₁₂ alkyl-C₆-C₁₂ aryl. X may be —O—, —S—, or —NH—; and n may beaninteger from 2 to 200. The polyol polyamido-β-ketoester composition mayinclude a compound represented by Formula XXVII:

At least one R^(1-XXVI) may be:

R² may be C₂-C₂₅ alkyl or C₂-C₂₅ alkenyl, optionally substituted with—OH or —NH₂. R⁴′ may be a bond; or C₁-C₂₅ alkyl, C₂-C₂₅ alkenyl, orC₂-C₂₅ epoxyalkyl, optionally substituted with —OH or —NH₂. R⁵ may beC₁-C₈ alkyl, C₂-C₈ alkenyl, C₆-C₁₀ aryl, or C₄-C₈ heteroaryl, optionallysubstituted with —OH or —NH₂. R¹¹ may be C₂-C₁₂ alkyl, C₆-C₁₂ aryl, orC₂-C₁₂ alkyl-C₆-C₁₂ aryl. X may be —O—, —S—, or —NH—. R^(13a) may be:

In some embodiments, the composition may include: the polyol unit; theβ-ketoester group bonded to the alkyl chain of the polyol unit; and theamine group bonded to the carbon on the alkyl chain that beta to theketone of the β-ketoester such that the poly(polyol)-β-ketoestercomposition includes the polyol polyamino-β-ketoester composition. Thepolyol polyamino-β-ketoester composition may include a compoundrepresented by Formula XXVIII:

R⁵ may be C₁-C₈ alkyl, C₂-C₈alkenyl, C₆-C₁₀ aryl, or C₄-C₈ heteroaryl,optionally substituted with —OH or —NH₂. R¹²′ may be C₂-C₆ alkyl, C₆-C₁₀aryl, C₁-C₆ alkyl-C₆-C₁₀ aryl, C₃-C₅ heteroaryl, or C₁-C₆ alkyl-C₃-C₅heteroaryl. R¹⁴ may be a polyol derived from one of: a pyrolyzedbio-oil, a modified triglyceride, and a triglyceride from a marineorganism. R¹²″ may be: C₁-C₁₂ alkyl, C₁-C₁₂ aryl, CH₂OH, CH₂OCH₃, CH₂SH,CH₂SCH₃,

The polyamino-β-ketoester composition may include a compound representedby Formula XXIX:

At least one R^(1-XXVIV) may be:

R² may be C₁-C₂₅ alkyl or C₂-C₂₅ alkenyl, optionally substituted with—OH or —NH₂. R⁴′ may be a bond; or C₁-C₂₅ alkyl, C₂-C₂₅ alkenyl, orC₂-C₂₅ epoxyalkyl, optionally substituted with —OH or —NH₂. R⁵ may beC₁-C₈ alkyl, C₂-C₈ alkenyl, C₆-C₁₀ aryl, or C₄-C₈ heteroaryl, optionallysubstituted with —OH or —NH₂. R¹¹ may be C₂-C₁₂ alkyl, C₆-C₁₂ aryl, orC₂-C₁₂ alkyl-C₆-C₁₂ aryl. X may be —O—, —S— or —NH—. R^(13b) may be:—OH, —OCH₃, —SH, —SCH₃,

In several embodiments, the composition may include: the polyol unit theβ-ketoester group bonded to the alkyl chain of the polyol unit; and thehydrazone group bonded to the keto-carbon of the β-ketoester group suchthat the poly(polyol)-β-ketoester composition includes the polyolpolyhydrazone-β-ketoester composition. The polyolpolyhydrazone-β-ketoester composition may include a compound representedby Formula XXX:

R⁵ may be C₁-C₈ alkyl, C₂-C₈ alkenyl, C₆-C₁₀ aryl, or C₄-C₈ heteroaryl,optionally substituted with —OH or —NH₂. R¹²′″ may be C₂-C₆ alkyl,C₆-C₁₀ aryl, C₁-C₆ alkyl-C₆-C₁₀ aryl, C₃-C₅ heteroaryl, or C₁-C₆alkyl-C₃-C₅ heteroaryl. R¹⁴ may be a polyol derived from one of: apyrolyzed bio-oil, a modified triglyceride, and a triglyceride from amarine organism. The polyol polyhydrazone-β-ketoester composition mayinclude a compound represented by Formula XXXI:

At least one R^(1-XXXI) may be:

R² may be C₂-C₂₅ alkyl or C₂-C₂₅ alkenyl, optionally substituted with—OH or —NH₂. R⁴′ may be a bond; or C₁-C₂₅ alkyl, C₂-C₂₅ alkenyl, orC₂-C₂₅ epoxyalkyl, optionally substituted with —OH or —NH₂. R¹¹ may beC₂-C₁₂ alkyl, C₂-C₈ alkenyl, C₆-C₁₀ aryl, or C₄-C₈ heteroaryl,optionally substituted with —OH or —NH₂. R¹¹ may be C₂-C₁₂ alkyl, C₆-C₁₂aryl, or C₂-C₁₂ alkyl-C₆-C₁₂ aryl. X may be —O—, —S—, or —NH—. R¹²′″ maybe C₂-C₆ alkyl, C₆-C₁₀ aryl C₁-C₆ alkyl-C₆-C₁₀ aryl, C₃-C₅ heteroaryl,or C₁-C₆ alkyl-C₃-C₅ heteroaryl. R¹³″ may be:

In various embodiments, the poly(polyol)-β-ketoester composition may bea product formed by a process according to any method described hereinfor the poly(polyol)-β-ketoester composition.

In various embodiments, an article is provided. The article may includea surface coated with a poly(AAG)-composition. e.g., as thepoly(AAG)-β-ketoester composition. The poly(AAG)-composition, e.g., asthe poly(AAG)-β-ketoester composition, may include any aspect of thepoly(AAG)-composition, e.g., as the poly(AAG)-β-ketoester composition,described herein, and may be a product formed by a process according toany method described herein for the poly(AAG)-composition, e.g., as thepoly(AAG)-β-ketoester composition. The article may be a beverage or foodcontainer and the poly(AAG)-composition, e.g., as thepoly(AAG)-β-ketoester composition, may form a coating on an interiorsurface of the beverage or food container. The surface may include afoil or metal packaging material. The surface may include one or moreof: low carbon steel aluminum, anodized aluminum, silver, and alloys ormixtures thereof. The surface may be one or more of: an interior surfaceor an exterior surface of a medical device. The poly(AAG)-composition,e.g., as the poly(AAG)-β-ketoester composition, may form a cross-linkedcoating on one or more of: the interior surface and the exterior surfaceof the medical device. Further, silver may be included by one or moreof: the interior surface, the exterior surface, and thepoly(AAG)-composition, e.g., as the poly(AAG)-β-ketoester composition,forming the cross-linked coating. The silver may be in ionic or oxideform.

EXAMPLES

The following examples illustrate the processes and compositions ofdescribed herein. The following examples are merely illustrative andshould not be construed to limit the scope of the embodiments describedherein in any way.

Example 1: Synthesis of Acetoacetoxy Amines Example1A—Tetraacetoacetoxyethylenediamine (TAAED)

A 250 mL 3-neck round bottom flask was charged with ethylene diamine(11.1 mL, 167 mmol) and t-butyl acetoacetate (110.4 mL, 666 mmol) andpurged with argon. The flask was fitted with a Dean-Stark trap, awater-cooled condenser, a thermocouple, and an overhead stirrer. Thesolution was brought to 150° C. and stirred under argon. Byproductt-butanol was collected in the trap. After 30 min, the temperature wasincreased to 160° C. and an exotherm to 170° C. was observed. After 40min, t-butanol (50.9 mL, 533 mmol, 80%) was collected and the dark red,molten mixture was allowed to cool to room temperature. The resultingred solid was manually broken to yield an orange-red powder.

Example 1B—Tetraacetoacetoxyethylenediamine (TAAED)

A 500 mL 3-neck round bottom flask was charged with ethylene diamine(5.6 mL, 84 mmol) and excess t-butyl acetoacetate (1.27 L, 7.63 mol) andpurged with argon. The flask was fitted with a Dean-Stark trap, awater-cooled condenser, a thermocouple, and an overhead stirrer. Thesolution was stirred at room temperature under argon for 30 min and anexotherm to 40° C. was observed. The reaction mixture was heated to 140°C. and the clear solution became yellow. While ramping the temperatureto 150° C., byproduct t-butanol (9 mL, 94.1 mmol) was collected in thetrap. After 1 b at 150° C., t-butanol (49 mL, 512 mmol, 97%) wascollected in the trap and the solution became dark red in color. Thesolution was allowed to cool to room temperature and excess startingmaterials were removed under reduced pressure. The product was analyzedby NMR and IR and was substantially the same as the product obtained inExample 1A.

Example 1C—Hexaacetoacetonoatemelamine (HAAM)

A 250 mL flask was charged with melamine (20 g), 1-butyl acetoacetate(150.51 g), and purged with argon. The flask was fitted with aDean-Stark trap, a water-cooled condenser, a thermocouple, and anoverhead stirrer. The solution was stirred and heated at 170° C. for 4h. Upon cooling, the solution became a hard, dark red solid. The productwas obtained in greater than 80% yield.

Example 2: Synthesis of Polyol-AAG (Acetoacetalation of Polyol) Example2A—Soy-AAG (“Soy-PK”)

A 1 L flask was charged with soy polyol (600.5 g) [Honeybee HB530, MCPUPolymer Engineering, LLC, Richmond. Va.] and t-butyl acetoacetate (156.7ml, 946 mmol), and purged with argon. The flask was fitted with aDean-Stark trap, a water-cooled condenser, a thermocouple, and anoverhead stirrer. The reaction was heated to 140° C. aid stirred for 4 hwhich resulted in byproduct t-butanol (100%) collected in the trap.Fourier Transform Infrared (FTIR) spectra of the Soy-AAG product wasobtained, as shown in FIG. 1. The peak at 1730 cm⁻¹ is characteristic ofthe acetoacetate functional group. The Soy-AAG product is a solid andmay be diluted with methyl ethyl ketone. The physical properties ofSoy-AAG is illustrated in tabular form in FIG. 2.

Example 2B—Soy-AAG (“Soy-PK”)

A 1 L flask was charged with soy polyol (690.5 g) [Honeybee HB530, MCPUPolymer Engineering, LLC] and t-butyl acetoacetate (156.7 mL, 946 mmol),and purged with argon. The flask was fitted with a Dean-Stark trap, awater-cooled condenser, a thermocouple, and an overhead stirrer. Thereaction was heated to 140° C. and stirred for 3 h which resulted inbyproduct t-butanol (73.3 mL, 766 mmol, 81%) collected in the trap. Thetemperature was increased to 150° C. and the reaction was stirred for anadditional 3 h. Byproduct i-butanol (100%) was collected. FourierTransform Infrared (FTIR) spectra of the product was obtained, as shownin FIG. 1. The peak at 1730 cm⁻¹ is characteristic of the acetoacetatefunctional group. The Soy-AAG product is a solid and may be diluted withmethyl ethyl ketone. The physical properties of Soy-AAG is illustratedin tabular form in FIG. 2.

Example 2C—Pentaerythritol-AAG

A 1 L flask was charged with pentaerythritol (40.5 g, 1.03 mol) andt-butyl acetoacetate (684.5 mL, 4.13 mol), and purged with argon. Theflask was fitted with a Dean-Stark trap, a water-cooled condenser, athermocouple, and an overhead stirrer. The reaction was heated to 140°C. for 4 h. The product was isolated without any further purification in94% yield.

Example 2D—Sucrose-AAG

A 250 mL flask was charged with sucrose (20.06 g, 58.6 mmol) and 1-butylacetoacetate (81.4 mL, 491 mmol), and purged with argon. The flask wasfitted with a Dean-Stark trap, a water-cooled condenser, a thermocouple,and an overhead stirrer. The reaction was heated at 150° C. for 2 h.After this time, the reflux ceased and the reaction temperature asincreased to 170° C. for an additional 2 h. Byproduct t-butanol (32.7mL, 342 mmol, 70%) was collected.

Example 2E—1,4-BD-diAAG

A 250 mL flask was charged with 1,4-butanediol (29.6 mL, 334 mmol) andt-butyl acetoacetate (116.6 mL, 703 mmol), and purged with argon. Theflask was fitted with a Dean-Stark trap, a water-cooled condenser, athermocouple, and an overhead stirrer. The reaction was heated at 150°C. for 4 h. Byproduct t-butanol (60.1 mL, 628 mmol, 89%) was collected.

Example 2F—Glycerol-triAAG

A flask was charged with glycerol (150.7 mL, 206 mmol) and t-butylacetoacetate (1.03 L, 6.19 mol), and purged with argon. The flask wasfitted with a Dean-Stark trap, a water-cooled condenser, a thermocouple,and an overhead stirrer. The reaction was heated to 140° C. After 3 ht-butanol (481.3 mL, 5.03 mol, 81%) was collected in the trap. Thetemperature was increased to 150° C. and the reaction was allowed tostir for an additional 3 h. Byproduct t-butanol (561.8 mL, 5.87 mol,95%) was collected.

Example 2G—Arsoy-AAG

A 250 mL flask was charged with jet-milled soy carbohydrate concentrate(30 g) (Arsoy, Praeter Industries MKBL4718V <20 micron) and t-butylacetoacetate (94.3 mL, 569 mmol), and purged with argon. The flask wasfitted with a Dean-Stark trap, a water-cooled condenser, a thermocouple,and an overhead stirrer. The reaction was heated at 140° C. for 4 h.Byproduct t-butanol (100%) was collected and a tan paste was obtained.

Example 2H—Stearyl-AAG

A 250 mL flask was charged with stearyl alcohol (80.0 g, 296 mmol),1-butyl acetoacetate (53.2 mL, 321 mmol), and purged under argon. Theflask was fitted with a Dean-Stark trap, a water-cooled condenser, athermocouple, and an overhead stirrer. The reaction mixture was heatedat a 150° C. for 4 h. By product t-butanol (20.9 mL, 218 mmol, 74%) wascollected in the trap.

Example 21—Polyesterpolyether Polyol-AAG

A 1 L round bottom flask was charged with Boltorn™ P501 (353 g)[Perstorp Winning Formulas. Perstorp, Sweden], t-butyl acetoacetate (377g), and purged under argon. The flask was fitted with a Dean-Stark trap,a water-cooled condenser, a thermocouple, and an overhead stirrer. Thereaction mixture was heated at 140° C. for 4 h. Byproduct t-butanol(96%) was collected in the trap.

Example 2J—Polyether Polyol-AAG

A 500 mL round bottom flask was charges with JEFFOL® SG360 (200.3 g)[Huntsman. Auburn Hills, Michigan], t-butyl acetoacetate (205.8 g), andpurged under argon. The flask was fitted with a Dean-Stark trap, awater-cooled condenser, a thermocouple, and an overhead stirrer. Thereaction mixture was heated at 140° C. for 2 h. Byproduct t-butanol(96%) was collected in the trap.

Example 3: Soy-AAG Polyamine and Soy-AAG Polyamide Coating

Examples 3A-3C below were performed as follows: The AAG and crosslinker(total 10 grams) were weighed in a Flecktec mixing cup along with PTSA(0.5-10 wt % in methyl ethyl ketone (MEK)). The contents were mixed at3000 rpm for 1 min. The resulting mixture was coated onto a low carbonsteel panel using a 2 mm wet film thickness drawdown bar. The panel wascured at 180° C. for 30 min.

Example 3A

75% soy-AAG: 25% CYMEL™ 303, PTSA (0.5%). It was observed fromThermogravimetric Analysis (TGA) that soy-AAG (“Soy-PK”) cures fasterthan its precursor: the non-acetoacetoatylated commercial bio-basedpolyol [Honeybee HB530, MCPU Polymer Engineering, LLC, Richmond]. TheTGA plot of soy-AAG curing with CYMEL™ 303 is compared with thebio-based soy polyol curing with CYMEL™ 303, as shown in FIG. 3.

The degree of cure, α, can be calculated from the TGA data using thefollowing equation:

$\mspace{79mu} {\alpha = \frac{\Delta \text{?}}{\Delta \; y}}$?indicates text missing or illegible when filed

where Δm_(t,T) is the difference in mass at time t and temperature T; Δyis the derivative at the given cure temperature T. The derivative at200° C. for soy-AAG and polyol-based resin is respectively 19.2 and17.9%. Therefore, the degree of cure at 20 min for soy-AAG is 51%, andthe degree of cure for the commercial bio-based polyol is 29%.

Performance data for the soy-AAG cured resin is illustrated in tabularformat in FIG. 4. The corrosion performance of soy-AAG cured resin wasevaluated using Electrochemical Impedance Spectroscopy (EIS). Thecoating was exposed to 3.5 wt % NaCl and the impedance was measuredusing a PAR potentiostat/galvanostat and Solartron equipment between thefrequency range of 0.01 Hz to 65 Hz. The total coating impedance at afrequency of 0.1 Hz was used as a guide to predict the corrosionperformance of die coating. The performance for the soy-AAG cured resincoating over a period of 50 days is shown in FIG. 5. It was evident thatthe soy-AAG cured resin is on par with the corrosion performance ofBPA-based resin and outperforms commercial bio-based BPA-freealternative coatings.

The toxicity of soy-AAG cured resin was assessed using BG1LUC assay, asdescribed in Bittner, et al., Environmental Heath, 2014, 13, 103. It wasfound that soy-AAG cured resin has no detectable estrogenic (see FIG. 6)or anti-estrogenic activity (see FIG. 7).

Example 3B

50% soy-AAG: 25% CYMEL™ 303: 25% pentaerythritol-AAG; PTSA (0.5%).

Example 3C

50% soy-AAG; 25% CYMEL® 303; 25% dipentaerythriol-AAG; PTSA (0.5%).

Example 3D

95% soy-AAG; 5% PMDI: 70% solids with MEK. The AAG and crosslinker(total 10 grams) was weighed in a Flecktec mixing cup along with methylethyl ketone. The contents were mixed at 3000 rpm for 1 min. Theresulting mixture was coated onto a low carbon steel panel using a 2 mmwet film thickness drawdown bar. The panel was cured at 180° C. for 30min.

Example 3E—Arsoy-AAG Polyamine

A flask was charged with CYMEL™ 303 (2.5 g), Arsoy-AAG 7.5 g), p-toluenesulfonic acid (0.5% wt). The mixture was diluted with MEK (30% wt) andstirred until a uniform solution was achieved. The solution was spreadonto a low carbon steel coupon (2 mm film thickness) and heated (cured)at 180° C. for 30 min. The resulting tackless coating appeared opaqueand yellow in color.

Example 3F—Styrenyl-AAG Polyamine

A flask was charged with CYMEL™-303 (2.5 g). Styrene-AAG of Example 5A(2.5 g), Soy-AAG of Example 2A/2B (5.0 g) and p-toluene sulfonic acid(0.2 mol %). The reaction mixture was stirred until a uniform solutionwas obtained. The reaction mixture was spread onto a low carbon steelcoupon (2 mm thick). The coupon and reaction mixture were heated at 180°C. for 30 min, resulting in a tackless yellow-brown film.

Example 4: Soy-AAG Polyamide Foam Example 4A

Soy-AAG (20.13 g), Luprinate M20 (6 g), tegostab B4690 (0.1 g), water(0.11 g) and MEK (2.1 g) were rapidly mixed using a spatula at about 23°C. for 2-4 min. The resulting mixture was poured into a container coatedwith a release agent and the foam solids were allowed to expand 5-15times.

Example 4B

Soy-AAG (20.01 g), Luprinate M20 (9.5 g), tegostab B4690 (0.2 g), water(1.01 g) and MEK (4 g) were rapidly mixed at about 23° C. for 2-4 min.The resulting mixture was poured into a container coated with releaseagent and the foam solids were allowed to expand 5-15 times.

Example 4C

Soy-AAG (20.01 g), Luprinate M2 (9.5 g), tegosab B4690 (0.2 g), andwater (1.01 g) were rapidly mixed at about 23° C. for 2-4 min. Theresulting mixture was poured into a container coated with release agentand the foam solids were allowed to expand 5-15 times.

Example 4D

Soy-AAG (30 g), Luprinate M20 (9.5 g), tegostab B4690 (0.2 g), water(0.5 g), and Mg(OH), (2.0 g) were rapidly mixed at about 23° C. for 2-4min. The resulting mixture was poured into a container coated withrelease agent and the foam solids were allowed to expand 5-15 times.

Example 4E

Soy-AAG (5.02 g). Luprinate M20 (9.5 g), tegostab B4690 (0.2 g), water(0.21 g), and glycerol-AAG (prepared according to Example 2) (1.35 g)were rapidly mixed at about 23° C. for 2-4 mm. The resulting mixture waspoured into a container coated with release agent aid the foam solidswere allowed to expand 5-15 times.

Example 5: Biomass Surrogate-AAG Example 5A—Styrene-AAG

A 500 mL flask was charged with 2-(methylacryloyloxy) ethyl acetoacetate(89.1 mL, 467 mmol), styrene 110 mL, 960 mmol), and AIBN (4.0 g, 24.4mmol), and purged with argon. The flask was fitted with a Dean-Starktrap, a water-cooled condenser, a thermocouple, and an overhead stirrer.The reaction was heated to 60° C. and stirred for 24 h. The reactionmixture was cooled and gave a pale yellow product with low viscosity.

Example 5B—Polyol-diAAG Diurethane

Hexamethylene diisocyanate (HDI) was reacted with ethylene glycol togive a hexamethylene diurethane diol. A 250 mL flask was charged withhexamethylene diurethane diol (48.62 g, 289 mmol) t-butyl acetoacetate(55.2 mL, 333 mmol), and purged under argon. The flask was fitted with aDean-Stark trap, a water-cooled condenser, a thermocouple, and anoverhead stirrer. The reaction mixture was heated to 140° C. for 2 h.Byproduct t-butanol (>90%) was collected in the trap. The reactionmixture was cooled to give a clear, yellow-orange product.

Example 5C—Polyol-diAAG Diurethane

A 500 mL flask was charged with hexamethylene diamine (110.7 g, 953mmol), ethylene carbonate (167.7 g, 1.9) mol), and purged under argon.The flask was fitted with a Dean-Stark trap, a water-cooled condenser, athermocouple, and an overhead stirrer. The reaction mixture was heatedto 90° C. for 20 h. The reaction mixture was cooled to give acrystalline solid.

Prophetic Example 6: Acetoacetalation of Epoxidized Triglyceride

To a solution of an epoxidized triglyceride, such as epoxidized soybeanoil, and choice solvent, may be added acetoacetic acid. The reaction maybe promoted by the addition of a mild, non-nucleophilic base.Alternatively, the reaction may be promoted by an acid catalyst.

Prophetic Example 7: Acetoacetalation of Unsaturated Triglyceride

To a solution of TAAED mid choice solvent, may be added an aqueoussolution of H₂O₂. The solution may be stirred for a period of timebefore the addition of a solution of an unsaturated triglyceride in achoice solvent. Alternatively, the TAAED/H₂O₂ solution may be added to aflask containing the unsaturated triglyceride solution. It is alsoconceivable that TAAED, H₂O₂, aid the unsaturated triglyceride may becombined at once, though it is presumed that higher yield may beobtainable in a step-wise fashion.

Prophetic Example 8: Acetoacetalation of Unsaturated Natural Oil

To a solution of TAAED mid choice solvent, may be added an aqueoussolution of H₂O₂. The solution may be stirred for a period of timebefore the addition of a solution of an unsaturated fatty acid ester ina choice solvent. Alternatively, the TAAEDH/H₂O₂ solution may be addedto a flask containing the unsaturated fatty acid ester. The TAAED, H₂O₂,and the fatty acid ester may be combined at once, though it is presumedthat higher yield may be obtainable in a step-wise fashion.

Prophetic Example 9: Pyrolized Bio-oil-AAG

A flask may be charged with alcohols and/or polyols of pyrolizedbio-oil, t-butyl acetoacetate, and purged under argon. The flask may befitted with a Dean-Stark trap, a water-cooled condenser, a thermocouple,and an overhead stirrer. The reaction mixture may be heated to 140-200°C. for a period of time. The byproduct t-butanol may be collected in thetrap and the quantity of t-butanol produced may be indicative of theprogression of the reaction.

To the extent that the term “include” or “including” is used in thespecification or the claims, it is intended to be inclusive in a mannersimilar to the interpretation of the term “comprising” when employed asa transitional word in a claim. Furthermore, to the extent that the term“or” is employed (e.g., A or B) it is intended to mean “A or B or both.”When “only A or B but not both” is intended, then the term “only A or Bbut not both” will be employed. Thus, use of the term “or” herein is theinclusive, and not the exclusive use. As used in the specification andthe claims, the singular forms “a,” “an,” and “the” include the plural.As used herein, the term “approximately” means plus or minus 10% unlessotherwise specified.

The terms “optional” and “optionally” mean that the subsequentlydescribed circumstance may or may not occur, so that the descriptionincludes instances where the circumstance occurs and instances where itdoes not.

In general, “substituted” refers to an organic group as defined below(e.g., an alkyl group) in which one or more bonds to a hydrogen atomcontained therein are replaced by a bond to non-hydrogen or non-carbonatoms. Substituted groups also include groups in which one or more bondsto a carbon(s) or hydrogen(s) atom are replaced by one or more bonds,including double or triple bonds, to a heteroatom. Thus, a substitutedgroup is substituted with one or more substituents, unless otherwisespecified. In some embodiments, a substituted group is substituted with1, 2, 3, 4, 5, or 6 substituents. Examples of substituent groupsinclude: halogens (i.e. F, Cl, Br, and I), hydroxyls, alkoxy, alkenoxy,aryloxy, aralkyloxy, heterocyclyloxy, and heterocyclylalkoxy groups;carbonyls (oxo): carboxyls; esters; urethanes oximes; hydroxylamines;alkoxyamines; aralkoxyamines; thiols; sulfides; sulfoxides: sulfones;sulfonyls; sulfonamides, amines; N-oxides; hydrazides, hydrazides;hydrazones, aides; amides; ureas; amidines; guanidines; enamines;imides; isocyanates; isothiocyanates; cyanates; thiocyanates; imines;nitro groups; nitriles (i.e., CN); and the like.

Substituted ring groups such as substituted cycloalkyl, aryl,heterocyclyl and heteroaryl groups also include rings and ring systemsin which a bond to a hydrogen atom is replaced with a bond to a carbonatom. Therefore, substituted cycloalkyl, aryl, heterocyclyl andheteroaryl groups may also be substituted with substituted orunsubstituted alkyl, alkenyl, and alkynyl groups as defined below.

Alkyl groups include straight chain and branched chain alkyl groupshaving from 1 to 12 carbon atoms, and typically from 1 to 10 carbons or,in some embodiments, from 1 to 8, 1 to 6, or 1 to 4 carbon atoms.Examples of straight chain alkyl groups include groups such as methyl,ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octylgroups. Examples of branched alkyl groups include, but are not limitedto, isopropyl, iso-butyl, sec-butyl, tert-butyl, neopentyl, isopentyl,and 2,2-dimethylpropyl groups. Representative substituted alkyl groupsmay be substituted one or more times with substituents such as thoselisted above and include, without limitation, haloalkyl (e.g.,trifluoromethyl), hydroxyalkyl, thioalkyl, aminoalkyl, alkylaminoalkyl,dialkylaminoalkyl, alkoxyalkyl, carboxyalkyl, and the like.

Cycloalkyl groups include mono-, bi- or tricyclic alkyl groups havingfrom 3 to 12 carbon atoms in the ring(s), or, in some embodiments, 3 to10, 3 to 8, or 3 to 4, 5, or 6 carbon atoms. Exemplary monocycliccycloalkyl groups include, but are not limited to, cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.In some embodiments, the cycloalkyl group has 3 to 8 ring members,whereas in other embodiments, the number of ring carbon atoms rangesfrom 3 to 5, 3 to 6, or 3 to 7. Bi- and tricyclic ring systems includeboth bridged cycloalkyl groups and fused rings, such as, but not limitedto, bicyclo[2.1.1]hexane, adamantyl, decalinyl, and the like Substitutedcycloalkyl groups may be substituted one or more times with non-hydrogenand non-carbon groups as defined above. However, substituted cycloalkylgroups also include rings that are substituted with straight or branchedchain alkyl groups as defined above. Representative substitutedcycloalkyl groups may be mono-substituted or substituted more than once,such as, but not limited to, 2,2-, 2,3-, 2,4-2,5- or 2,6-disubstitutedcyclohexyl groups, which may be substituted with substituents such asthose listed above.

Aryl groups are cyclic aromatic hydrocarbons that do not containheteroatoms. Aryl groups herein include monocyclic, bicyclic andtricyclic ring systems. Thus, aryl groups include, but are not limitedto, phenyl, azulenyl, heptalenyl, biphenyl, fluorenyl, phenanthrenyl,anthracenyl, indenyl, indanyl, pentalenyl, and naphthyl groups. In someembodiments, aryl groups contain 6-14 carbons, and in others from 6 to12 or even 6-10 carbon atoms in the ring portions of the groups. In someembodiments, the aryl groups are phenyl or naphthyl. Although the phrase“aryl groups” includes groups containing fused rings, such as fusedaromatic-aliphatic ring systems (e.g., indanyl, tetrahydronaphthyl, andthe like), it does not include aryl groups that have other groups, suchas alkyl or halo groups, bonded to one of the ring members. Rather,groups such as tolyl are referred to as substituted aryl groups.Representative substituted aryl groups may be mono-substituted orsubstituted more than once. For example, monosubstituted aryl groupsinclude, but are not limited to, 2-, 3-, 4-, 5-, or 6-substituted phenylor napthyl groups, which may be substituted with substituents such asthose listed above.

Aralkyl groups are alkyl groups as defined above in which a hydrogen orcarbon bond of an alkyl group is replaced with a bond to an aryl groupas defined above. In some embodiments, aralkyl groups contain 7 to 16carbon atoms, 7 to 14 carbon atoms, or 7 to 10 carbon atoms. Substitutedaralkyl groups may be substituted at the alkyl, the aryl or both thealkyl and aryl portions of the group. Representative aralkyl groupsinclude but are not limited to benzyl and phenethyl groups and fused(cycloalkylaryl)alkyl groups such as 4-indanylethyl. Representativesubstituted aralkyl groups may be substituted one or more times withsubstituents such as those listed above.

Heterocyclic groups include aromatic (also referred to as heteroaryl)and non-aromatic ring compounds containing 3 or more ring members ofwhich one or more is a heteroatom such as, but not limited to, N, O, andS. In some embodiments, the heterocyclyl group contains 1, 2, 3 or 4heteroatoms. In some embodiments, heterocyclic groups include mono-, bi-and tricyclic rings having 3 to 16 ring members, whereas other suchgroups have 3 to 6, 3 to 10, 3 to 12, or 3 to 14 ring members.Heterocyclic groups encompass aromatic, partially unsaturated andsaturated ring systems, such as, for example, imidazolyl, imidazolinyland imidazolidinyl groups. The phrase “heterocyclic group” includesfused ring species including those comprising fused aromatic andnon-aromatic groups, such as, for example, benzotriazolyl,2,3-dihydrobenzo[1,4]dioxinyl, and benzo[1,3]dioxolyl. The phrase alsoincludes bridged polycyclic ring systems containing a heteroatom suchas, but not limited to, quinuclidyl. However, the phrase does notinclude heterocyclic groups that have other groups, such as alkyl, oxoor halo groups, bonded to one of the ring members. Rather, these arereferred to as “substituted heterocyclic groups.” Heterocyclic groupsinclude, but are not limited to, aziridinyl, azetidinyl, pyrrolidinyl,imidazolidinyl, pyrazolidinyl, thiazolidinyl, tetrahydrothiophenyl,tetrahydrofuranyl, dioxolyl, furanyl, thiophenyl, pyrolyl, pyrrolinylimidazolyl, imidazolinyl, pyrazolyl, pyrazolinyl, triazolyl, tetrazolyl,oxazolyl, isoxazolyl, thiazolyl, thiazolinyl, isothiazolyl,thiadiazolyl, oxadiazolyl, piperidyl, piperazinyl, norpholinyl,thiomorpholinyl, tetrahydropyranyl, tetrahydrothiopyranyl, oxathiane,dioxyl, dithianyl, pyranyl, pyridyl, pyrimidinyl, pyridazinyl,pyrazinyl, triazinyl, dihydropyridyl, dihydrodithiinyl,dihydrodithionyl, homopiperazinyl, quinuclidyl, indolyl, indolinyl,isoindolyl, azaindolyl (pyrrolopyridyl), indazolyl, indolizinyl,benzotriazolyl, benzinidazolyl, benzofuranyl, benzothiophenyl,benzthiazolyl, benzoxadiazolyl, benzoxawnyl, benzodithiinyl,benzoxathiinyl, benzothiainyl, benzoxazolyl, benzothiazolyl,benzothiadiazolyl, benzo[1,3]dioxolyl, pyrazolopyridyl, imidazopyridyl(azabenzimidazolyl), triazolopyridyl, isoxazolopyridyl, purinyl,xanthinyl, adeninyl, guaninyl, quinolinyl, isoquinolinyl, quinolizinyl,quinoxalinyl, quinazolinyl, cinnolinyl, phthalazinyl, naphthyridinyl,pteridinyl, thianaphthyl, dihydrobenzothiazinyl, dihydrobenzofuranyl,dihydroindolyl, dihydrobenzodioxinyl, tetrahydroindolyl,tetrahydroindazolyl, tetrahydrobenzimidazolyl, tetrahydrobenzotriazolyl,tetrahydropyrrolopyndyl, tetrahydropyrazolopyridyl,tetrahydroimidazopyridyl, tetrahydrotriazolopyridyl, andtetrahydroqunolinyl groups. Representative substituted heterocyclicgroups may be mono-substituted or substituted more than once, such as,but not limited to, pyridyl or morpholinyl groups, which are 2-, 3-, 4-,5-, or 6-substituted, or disubstituted with various substituents such asthose listed above.

Heteroaryl groups are aromatic ring compounds containing 5 or more ringmembers, of which one or more is a heteroatom such as, but not limitedto, N, O, and S. Heteroaryl groups include, but are not limited to,groups such as pyrrolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl,isoxazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidimyl, pyrazinyl,thiophenyl, benzothiophenyl, furanyl, benzofuranyl, indolyl, azaindol(pyrrolopyridinyl), indazolyl, benzimidazolyl, imidazopyridinyl(azabenzimidazolyl), pyrazolopyridinyl, triazolopyridinyl,benzotnazolyl, benzoxazolyl, benzothiazolyl, benzothiadiazolyl,imidazopyridinyl, isoxazolopyridinyl, thianaphthyl purinyl, xanthinyl,adeninyl, guaninyl, quinolinyl, isoquinolinyl, tetrahydroquinolinyl,quinoxalinyl, and quinazolinyl groups. Heteroaryl groups include fusedring compounds in which all rings are aromatic such as indolyl groupsand include fused ring compounds in which only one of the rings isaromatic, such as 2,3-dihydro indolyl groups. Although the phrase“heteroaryl groups” includes fused ring compounds, the phrase does notinclude heteroaryl groups that have other groups bonded to one of thering members, such as alkyl groups. Rather, heteroaryl groups with suchsubstitution are referred to as “substituted heteroaryl groups.”Representative substituted heteroaryl groups may be substituted one ormore times with various substituents such as those listed above.

Heteroaralkyl groups are alkyl groups as defined above in which ahydrogen or carbon bond of an alkyl group is replaced with a bond to aheteroaryl group as defined above. Substituted heteroaralkyl groups maybe substituted at the alkyl, the heteroaryl or both the alkyl andheteroaryl portions of the group. Representative substitutedheteroaralkyl groups may be substituted one or more times withsubstituents such as those listed above.

Groups described herein having two or more points of attachment (i.e.,divalent, trivalent, or polyvalent) within the compound of thetechnology are designated by use of the suffix, “ene.” For example,divalent alkyl groups are alkylene groups, divalent aryl groups arearylene groups, divalent heteroaryl groups are heteroarylene groups, andso forth. Substituted groups having a single point of attachment to thecompound of the technology are not referred to using the “ene”designation. Thus, for example, chloroethyl is not referred to herein aschloroethylene.

Alkoxy groups are hydroxyl groups (—OH) in which the bond to thehydrogen atom is replaced by a bond to a carbon atom of a substituted orunsubstituted alkyl group as defined above. Examples of linear alkoxygroups include, but are not limited to, methoxy, ethoxy, propoxy,butoxy, pentoxy, hexoxy, and the like. Examples of branched alkoxygroups include, but are not limited to, isopropoxy, sec-butoxy,tert-butoxy, isopentoxy, isohexoxy, and the like. Examples ofcycloalkoxy groups include, but are not limited to, cyclopropyloxy,cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, and the like.Representative substituted alkoxy groups may be substituted one or moretimes with substituents such as those listed above.

The term “amine” (or “amino”), as used herein, refers to NR^(a)R^(b)groups, wherein R^(a) and R^(b) are independently hydrogen, or asubstituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl,aralkyl, heterocyclylalkyl or heterocyclyl group as defined herein. Insome embodiments, the amine is alkylamino, dialkylamino, arylamino, oralkylarylamino. In other embodiments, the amine is NH₂, methylamino,dimethylamino, ethylamino, diethylamino, propylamino, isopropylamino,phenylamino, or benzylamino. The term “alkylamino” is defined asNR^(c)R^(d) wherein at least one of R^(c) and R^(d) is alkyl and theother is alkyl or hydrogen. The term “arylamino” is defined asNR^(e)R^(f), wherein at least one of R^(c) and R^(f) is aryl and theother is aryl or hydrogen.

The term “halogen” or “halo,” as used herein, refers to bromine,chlorine, fluorine, or iodine. In some embodiments, the halogen isfluorine. In other embodiments, the halogen is chlorine or bromine.

While the present application has been illustrated by the description ofembodiments, and while the embodiments have been described inconsiderable detail, it is not the intention to restrict or in any waylimit the scope of the appended claims to such detail. Additionaladvantages and modifications will readily appear to those skilled in thean, having the benefit of this application. Therefore, the application,in its broader aspects, is not limited to the specific details andillustrative examples shown. Departures may be made from such detailsand examples without departing from the spirit or scope of the generalinventive concept.

1. A method for preparing an acetoacetyl group (AAG) compositioncomprising: providing a poly-functional compound comprising two or morefunctional groups, each functional group independently being hydroxy,amino, or alkenyl, provided that the poly-functional compound is not atriglyceride-derived oil; and reacting the poly-functional compoundunder conditions effective to form the AAG composition by one or moreof: contacting the poly-functional compound with a ketene compound,wherein the poly-functional compound comprises at least one hydroxygroup; contacting the poly-functional compound with a β-ketoester,wherein the poly-functional compound comprises at least one hydroxy oramino group; contacting the poly-functional compound with a peroxoreagent and one or more of: a β-ketoimide, a β-ketoester, and aβ-ketoacid, wherein the poly-functional compound comprises at least onealkenyl group; and contacting the poly-functional compound with amercaptoalkanol in the presence of an initiator effective to form amercaptoalkanol-substituted compound, the poly-functional compoundcomprising at least one alkenyl group; and further reacting themercaptoalkanol-substituted compound with one or more of: theβ-ketoester and the β-ketoacid.
 2. The method of claim 1, comprising:contacting the poly-functional compound with the β-ketoester to form areaction mixture, the poly-functional compound comprising one or moreof: the hydroxyl group; and the amino group; and allowing thepoly-functional compound and the β-ketoester to react substantially inthe absence of solvent effective to form the AAG composition.
 3. Themethod of claim 1, comprising conducting the method substantially in theabsence of solvent.
 4. The method of claim 1, further comprisingremoving an alcohol byproduct by one or more of: distillation, reducedpressure, and contact with a molecular sieve.
 5. The method of claim 1,comprising reacting under an inert atmosphere.
 6. The method of claim 1,comprising reacting at a temperature in ° C. of at least about one ormore of: 120, 130, 140, 150, 160, 170, 180, 190, and
 200. 7. The methodof claim 1, comprising reacting for a period of time in hours of atleast about one or more of: 0.25, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,15, 20, and
 24. 8. The method of claim 1, at least a portion of thepoly-functional compound being a polyol derived from a pyrolyzedbio-oil.
 9. The method of claim 8, the pyrolyzed bio-oil being derivedfrom pyrolysis of one or more of: hardwood, softwood, grass, reeds,bagasse, sugarcane, corn stover, and sorghum.
 10. The method of claim 1,at least a portion of the poly-functional compound being a polyolderived from alkoxylated pyrolyzed bio-oil.
 11. The method of claim 1,at least a portion of the poly-functional compound comprising one ormore of: a phenol, a cresol, a guaiacol, aid a syringol.
 12. The methodof claim 1, at least a portion of the poly-functional compoundcomprising one or more of: pyrogallol, catechol, resorcinol,hydroquinone, lignin, and diphenolic acid.
 13. The method of claim 1, atleast a portion of the poly-functional compound comprising anunsaturated non-triglyceride oil derived from a marine organism, amammal, and an insect.
 14. The method of claim 12, the marine organismcomprising one or more of: algae, water hyacinth, bacteria, and diatoms.15. The method of claim 1, the poly-functional compound comprisinglignin or derivatives thereof.
 16. The method of claim 1, thepoly-functional compound comprising a petroleum derived polyol, apetroleum-derived polyamine, a petroleum-derived polyalkene, or acomposite or combination thereof.
 17. The method of claim 1, thepoly-functional compound being a polyol and the AAG being a polyol-AAG.18. The method of claim 1, the poly-functional compound comprising aC₂-C₂₀ compound substituted with at least one hydroxyl group.
 19. Themethod of claim 1, at least a portion of the poly-functional compoundbeing a polyol derived from a hydroxyl-containing fatty acid ester. 20.The method of claim 1, the ketene compound comprising one or more of:4-methyleneoxetan-2-one, 4-ethylidene-3-methyloxetan-2-one, and4-benzylidene-3-phenyloxetane-2-one.
 21. The method of claim 1, theketene compound derived from one or more of: an α-diazo ketone and anα-halo acyl halide.
 22. The method of claim 1, the ketene compound beingoptionally substituted with one or more of: C₁-C₈ alkyl and C₆-C₁₀ aryl.23. The method of claim 1, the β-ketoester being represented by FormulaXIV:

wherein: R″ is C₁-C₈ alkyl or C₆-C₁₀ aryl; R⁵ is C₁-C₈ alkyl, C₂-C₈alkenyl, C₆-C₁₀ aryl, or C₄-C₈ heteroaryl, optionally substituted with—OH or —NH₂; and R⁸ is H, C₁-C₈ alkyl, or C₆-C₁₀ aryl.
 24. The method ofclaim 1, the peroxo reagent comprising one or more of: hydrogenperoxide, manganese dioxide, sodium percarbonate, potassiumpercarbonate, sodium perborate, and potassium perborate.
 25. The methodof claim 1, the β-ketoimide being represented by Formula VI:

wherein: R⁵ is optionally hydroxylated C₁-C₈ alkyl, C₂-C₈ alkenyl,C₆-C₁₀ aryl, or C₄-C₈ heteroaryl; and R⁹ is C₁-C₈ alkyl or C₆ aryloptionally substituted with one or more of: nitro, carbonyl, haloalkyl,and halogen.
 26. The method of claim 18, the β-ketoimide beingrepresented by Formula VII:

wherein R⁵ is optionally hydroxylated C₁-C₈ alkyl, C₂-C₈ alkenyl, C₆-C₁₀aryl, or C₄-C₈ heteroaryl, and R¹⁰ is a C₂-C₆ alkyl, C₃-C₅ heteroaryl,or C₆ aryl optionally substituted with one or more of: nitro, carbonyl,halogen, and haloalkyl.
 27. The method of claim 1, the β-ketoimide beingrepresented by Formula VIII:


28. The method of claim 1, the β-ketoimide being represented by FormulaVIV:

wherein: R⁵ is optionally hydroxylated C₁-C₈ alkyl, C₂-C₈ alkenyl,C₆-C₁₀ aryl, or C₄-C₈ heteroaryl.
 29. The method of claim 1, theβ-ketoacid being represented Formula III:

wherein: R⁵ is optionally hydroxylated C₁-C₈ alkyl, C₂-C₈ alkenyl,C₆-C₁₀ aryl, or C₄-C₁₀ heteroaryl; and R⁸ is H, or optionallyhydroxylated C₁-C₈ alkyl or C₆-C₁₀ aryl.
 30. The method of claim 1, theβ-ketoacid comprising one or more of: 3-oxobutanoic acid, 3-oxopentanoicacid, 3-oxohexanoic acid, and 3-oxo-3-phenylpropanoic acid.
 31. Themethod of claim 1, the mercaptoalkanol comprising thio glycerol ormercaptoethanol.
 32. The method of claim 1, comprising: contacting thepoly-functional compound in the form of an unsaturated polyol with theperoxo reagent and the β-ketoimide to form a reaction mixture; andallowing the unsaturated polyol, the peroxo reagent, and the β-ketoimideto react effective to form the AAG composition as a polyol-AAGcomposition
 33. The method of claim 32, further comprising pre-mixingthe peroxo reagent and the β-ketoimide prior to contacting theunsaturated polyol.
 34. The method of claim 33, further comprisingpre-mixing the peroxo reagent and the β-ketoimide at a temperature lessthan about 25° C.
 35. The method of claim 32, further comprisingpre-mixing the unsaturated polyol and the β-ketoimide prior tocontacting the peroxo reagent.
 36. The method of claim 32, comprisingallowing the unsaturated polyol, the peroxo reagent, and the β-ketoimideto react at a temperature in ° C. of at least about one or more of: 0,10, 20, 30, 40, 50, 60, 70, 80, 90, and
 100. 37. The method of claim 32,comprising allowing the unsaturated polyol, the peroxo reagent, and theβ-ketoimide to react for a period of time in minutes of at least aboutone or more of: 5, 10, 15, 20, 30, 40, 60, 90, 120, 150, 170, and 200.38. The method of claim 32, further comprising, after forming thepolyol-AAG composition, contacting the reaction mixture with a reducingagent effective to consume at least a portion of remaining peroxoreagent.
 39. The method of claim 1, further comprising, after formingthe AAG composition, purifying the AAG composition by one or more of:contacting the reaction mixture with one of: water, aqueous brine, andaqueous mild acid; separating an aqueous layer from the reactionmixture; contacting the reaction mixture to a chromatography solidphase; and eluting the polyol-AAG composition from the chromatographysolid phase to provide the polyol-AAG composition in at least partlypurified form.
 40. The method of claim 32, the polyol-AAG compositioncomprising: a polyol unit; at least one hydroxyl group bonded to analkyl chain of the polyol unit; and a β-ketoester group bonded to acarbon atom of the alkyl chain that is alpha to a carbon atom bearingthe hydroxyl group.
 41. The method of claim 32, the polyol-AAGcomposition comprising a hydroxyl value greater than the unsaturatedpolyol.
 42. A method for preparing a poly(AAG)-composition, comprisingcontacting an AAG composition with a cross-linking compound to form areaction mixture, provided that the AAG composition is not atriglyceride-AAG composition and allowing the AAG composition and thecross-linking compound to react effective to form the poly(AAG)composition.
 43. The method of claim 42, comprising: contacting the AAGcomposition with the cross-linking compound to form the reactionmixture, the AAG composition being a AAG-β-ketoester composition; andallowing the AAG composition and the cross-linking compound to reacteffective to form the poly(AAG)-β-ketoester composition.
 44. The methodof claim 42, the AAG composition being derived from pyrolyzed bio-oil.45. The method of claim 44, the pyrolyzed bio-oil being derived frompyrolysis of one or more of: hardwood, softwood, grass, reeds, bagasse,corn stover, sugarcane, and sorghum.
 46. The method of claim 42, the AAGcomposition being derived from one or more of: a phenol, a cresol, aguaiacol, and a syringol.
 47. The method of claim 42, the AAGcomposition being derived from an alkoxylated pyrolyzed bio-oil.
 48. Themethod of claim 42, the AAG composition being derived from ahydroxyl-containing fatty acid ester.
 49. The method of claim 42,further comprising contacting the AAG composition with the cross-linkingcompound in the presence of a surfactant.
 50. The method of claim 42,allowing the AAG composition and the cross-linking compound to react ata temperature in C of at least about one or more of: 140, 150, 160, 170,180, 190, and
 200. 51. The method of claim 42, allowing the AAGcomposition and the cross-linking compound to react for a period of timein minutes of at least about one or more of: 5, 10, 15, 20, 25, 30, 35,40, 45, 50, 55, and
 60. 52. The method of claim 42, further comprisingcontacting the AAG composition with the cross-linking compound in thepresence of one or more of: an inert atmosphere; water; a blowing agent;and a base.
 53. The method of claim 52, the base comprising one or moreof: magnesium hydroxide, zirconium hydroxide, and aluminum hydroxide.54. The method of claim 42, further comprising: applying the reactionmixture to a surface; and heating the reaction mixture and the surfaceeffective to form the poly(AAG)-composition as a cross-linked coating onthe surface.
 55. The method of claim 54, further comprising: contactingthe AAG composition and the cross-linking compound to form the reactionmixture at about 25° C. for less than 3 minutes; applying the reactionmixture onto the surface; and heating the reaction mixture and thesurface at a temperature of about 180° C. for 30 minutes effective toform the poly(AAG)-composition as a cross-linked coating on the surface.56. The method of claim 55, the surface being a metal surface.
 57. Themethod of claim 55, the surface being an interior surface of a food orbeverage container.
 58. The method of claim 55, the surface comprising afoil or metal packaging material.
 59. The method of claim 55, thesurface comprising one or more of: low carbon steel, aluminum, anodizedaluminum, silver, and alloys or mixtures thereof.
 60. The method ofclaim 42, further comprising: contacting the AAG composition and thecross-linking compound at about 25° C., and pouring the reaction mixtureinto a mold, the mold coated in a mold release agent.
 61. The method ofclaim 42, the cross-linking compound comprising one or more of: adiisocyanate, a triisocyanate, and a tetraisocyanate.
 62. The method ofclaim 42, the cross-linking compound comprising a polymer comprisingmore than one isocyanate group.
 63. The method of claim 42, thecross-linking compound comprising one or more isocyanate cross-linkingreagents.
 64. The method of claim 42, the poly(AAG)-compositioncomprising: a polyol-polyamido-β-ketoester comprising: a polyol unit; aβ-ketoester group located on an alkyl chain of the polyol unit; and anamide group bonded to a carbon of the alkyl chain that is alpha to aketone of the β-ketoester.
 65. The method of claim 42, the cross-linkingcompound comprising one or more of: a hemiaminal, a hemiaminal ether, ahemiaminal thioether an aromatic hemiaminal, an aromatic hemiaminalether, an aromatic hemiaminal thioether, a polymer comprising ahemiaminal, a polymer comprising a hemiaminal ether, and a polymercomprising a hemiaminal thioether.
 66. The method of claim 42, thecross-linking agent comprising a hemiaminal crosslinking reagent. 67.The method of claim 42, further comprising contacting the AAGcomposition with the cross-linking compound in the presence of an acidcatalyst.
 68. The method of claim 67, the acid catalyst comprising oneor more of: p-toluene sulfonic acid; methane sulfonic acid; a C₁-C₈carboxylic acid; a C₁-C₈ halocarboxylic acid; and a polymeric sulfonicacid resin.
 69. The method of claim 42, further comprising contactingthe AAG composition with the cross-linking compound in the presence of aLewis acid catalyst.
 70. The method of claim 42, further comprisingremoving an alcohol byproduct from the reaction mixture by one or moreof: distillation, reduced pressure, and contact with a molecular sieve.71. The method of claim 42, the AAG composition comprising: a polyolpolyamino-β-ketoester comprising: a polyol unit; a β-ketoester groupbonded to an alkyl chain of the polyol unit; and an amine group bondedto a carbon beta to a ketone of the β-ketoester.
 72. The method of claim42, the cross-linking compound comprising a polyamine.
 73. The method ofclaim 42, the cross-linking compound comprising one or more of: adihydrazine and a dihydrazide.
 74. The method of claim 72, thecross-linking compound comprising one or more of: adipic dihydrazide,sebacic dihydrazide, oxalyl dihydrazide, succinic dihydrazide, maleicdihydrazide, malic dihydrazide, isophthalic dihydrazide, andterephthalic dihydrazide.
 75. The method of claim 42, the AAGcomposition comprising: a polyol polyeneamine-β-ketoester comprising: apolyol unit; a β-ketoester group bonded to an alkyl chain of the polyolunit; and an enamine bonded to a keto-carbon of the β-ketoester andeffective to cross-link more than one polyol unit.
 76. The method ofclaim 42, the AAG composition comprising: a polyolpolyhydrazone-β-ketoester comprising: a polyol unit; a β-ketoester groupbonded to an alkyl chain of the polyol unit; and a hydrazone bonded to aketo-carbon of the β-ketoester and effective to cross-link more than onepolyol unit.
 77. The method of claim 42, the cross-linking compoundcomprising at least two diazonium groups, the diazonium groups beingeffective to cross-link two or more AAG compounds of the AAG compositionto form azo cross-links.
 78. The method of claim 42, the cross-linkingcompound comprising an aldehyde, the aldehyde being effective tocross-link two or more AAG compounds of the AAG composition through amethylene cross-link.
 79. The method of claim 78, the aldehyde beingformaldehyde.
 80. The method of claim 42, the cross-linking compoundcomprising at least two α,β-unsaturated carbonyls, the α,β-unsaturatedcarbonyls effective to cross-link two or more AAG compounds of the AAGcomposition.
 81. The method of claim 80, the cross-linking compoundbeing represented by Formula XIV:

wherein R is CH₂CH₂, CH₂(CH₃)CH, (CH₂CH₂OCH₂CH₂)_(n), or(CH₂(CH₃)CHOCH₂(CH₃)CH)_(n); and n is an integer from 1 to
 50. 82. Apoly(AAG)-composition, comprising: a polyfunctional moiety derived froma polyol unit, a polyamine unit, a polyalkene unit, or a combination orcomposite thereof; a β-ketoester group bonded to an alkyl chain of thepolyfunctional moiety; and one or more of: an amide group bonded to acarbon of the alkyl chain that is alpha to a ketone of the β-ketoestersuch that the poly(AAG)-composition comprises apoly(AAG)amido-β-ketoester composition; an amine group bonded to acarbon on the alkyl chain that is beta to a ketone of the β-ketoestersuch that the poly(AAG)-composition comprises apoly(AAG)amino-β-ketoester composition; and a hydrazone group bonded toa keto-carbon of the β-ketoester group such that thepoly(AAG)-composition comprises a poly(AAG)hydrazone-β-ketoestercomposition.
 83. The composition of claim 82, the poly(AAG)-compositionbeing a ly(polyol)-β-ketoester composition, comprising: thepolyfunctional moiety in the form of the polyol unit; the β-ketoestergroup bonded to an alkyl chain of the polyol unit; and one or more of:the amide group bonded to the carbon of the alkyl chain that is alpha tothe ketone of the β-ketoester such that the poly(polyol)-β-ketoestercomposition comprises a polyol polyamido-β-ketoester composition; theamine group bonded to the carbon on the alkyl chain that is beta to theketone of the β-ketoester such that the poly(polyol)-β-ketoestercomposition comprises a polyol polyamino-β-ketoester composition; andthe hydrazone group bonded to the keto-carbon of the β-ketoester groupsuch that the poly(polyol)-β-ketoester composition comprises a polyolpolyhydrazone-β-ketoester composition.
 84. The poly(AAG)-composition ofclaim 82, being in the form of one or more of: a cross-linked coatingand a cross-linked foam.
 85. The poly(AAG)-composition of claim 82,being in the form of a cross-linked coating on a surface.
 86. Thepoly(AAG)-composition of claim 82, being in the form of a cross-linkedcoating on a metal surface.
 87. The poly(AAG)-composition of claim 82,being in the form of a cross-linked coating on an interior surface of abeverage or food container.
 88. The poly(AAG)-composition of claim 82,being in the form of a cross-linked coating on one or more of: a foil ormetal packaging material.
 89. The poly(AAG)-composition of claim 82,being in the form of a cross-linked coating on one or more of: lowcarbon steel, aluminum, anodized aluminum, silver, and alloys ormixtures thereof.
 90. The poly(AAG)-composition of claim 82, comprising:the polyol unit; the β-ketoester group bonded to am alkyl chain of thepolyol unit; and the amide group bonded to the carbon of the alkyl chainthat is alpha to the ketone of the β-ketoester such that thepoly(AAG)-β-ketoester composition comprises a polyolpolyamido-β-ketoester composition.
 91. The composition of claim 90, thepolyol polyamido-β-ketoester composition comprising a compoundrepresented by Formula XXV:

wherein: R⁵ is C₁-C₈ alkyl, C₂-C₈ alkenyl, C₆-C₁₀ aryl, or C₄-C₈heteroaryl, optionally substituted with —OH or —NH₂; R¹² is C₂-C₆ alkyl,C₆-C₁₀ aryl, C₁-C₆ alkyl-C₆-C₁₀ aryl, C₃-C₅ heteroaryl, or C₁-C₆alkyl-C₃-C₅ heteroaryl; and R¹⁴ is a polyol derived from one of: apyrolyzed bio-oil, a modified triglyceride, and a triglyceride from amarine organism.
 92. The poly(AAG)-composition of claim 82, comprising:the polyol unit; the β-ketoester group bonded to the alkyl chain of thepolyol unit; and the amine group bonded to the carbon on the alkyl chainthat is beta to the ketone of the β-ketoester such that thepoly(AAG)-composition comprises a polyol polyamino-β-ketoestercomposition.
 93. The composition of claim 92, the polyolpolyamino-β-ketoester composition comprising a compound represented byFormula XXVIII:

wherein: R⁵ is C₁-C₈ alkyl, C₂-C₈ alkenyl, C₆-C₁₀ aryl, or C₄-C₈heteroaryl, optionally substituted with —OH or —NH₂; R¹²′ is C₂-C₆alkyl, C₆-C₁₀ aryl, C₁-C₆ alkyl-C₆-C₁₀ aryl, C₃-C₅ heteroaryl, or C₁-C₆alkyl-C₃-C₅ heteroaryl; R¹⁴ is a polyol derived from one of: a pyrolyzedbio-oil, a modified triglyceride, and a triglyceride from a marineorganism; and R¹²″ is: C₁-C₁₂ alkyl, C₁-C₁₂ aryl, CH₂OH, CH₂OCH₃, CH₂SH,CH₂SCH₃,


94. The poly(AAG)-composition of claim 82, comprising: the polyol unit;the β-ketoester group bonded to the alkyl chain of the polyol unit; andthe hydrazone group bonded to the keto-carbon of the β-ketoester groupsuch that the poly(AAG)-β-ketoester composition comprises the polyolpolyhydrazone-β-ketoester composition.
 95. The composition of claim 94,the polyol hydrazone-β-ketoester composition comprising a compoundrepresented by Formula XXX:

wherein R⁵ is C₁-C₈ alkyl, C₂-C₈ alkenyl, C₆-C₁₀ aryl, or C₄-C₈heteroaryl, optionally substituted with —OH or —NH₂; R¹²′″ is C₂-C₆alkyl, C₁-C₆ aryl, C₁-C₆ alkyl-C₆-C₁₀ aryl, C₃-C₅ heteroaryl, or C₁-C₆alkyl-C₃-C₅ heteroaryl; and R¹⁴ is a polyol derived from a pyrolyzedbio-oil.
 96. The poly(AAG)-composition of claim 82, formed by the methodof any of claims 42 to
 81. 97. An article comprising a surface coatedwith a poly(AAG)-composition.
 98. The article of claim 96, thepoly(AAG)-composition being the poly(AAG)-composition of any of claims82 to
 96. 99. The article of claim 97, the poly(AAG)-composition beingformed according to the method of any of claims 42 to
 81. 100. Thearticle of claim 97, the article being a beverage or food container andthe surface comprising an interior surface of the beverage or foodcontainer, the poly(AAG)-composition forming a cross-linked coating onthe interior surface of the beverage or food container.
 101. The articleof claim 97, the article being a medical device and the surfacecomprising one or more of an interior surface and an exterior surface ofthe medical device, the poly(AAG)-composition forming a cross-linkedcoating on one or more of the interior surface and the exterior surfaceof the medical device.
 102. The article of claim 101, further comprisingsilver comprised by one or more of: the interior surface; the exteriorsurface; and the poly(AAG)-composition forming the cross-linked coating.103. The article of claim 101, comprising the silver in ionic or oxideform.